Catalyst and process for the hydrogenitrogenation and hydrocracking of high-nitrogen feeds

ABSTRACT

There is disclosed a catalyst, which catalyst comprises a hydrogenation component comprising chromium, molybdenum, and at least one metal of Group VIII, a crystalline molecular sieve zeolite, and a porous refractory inorganic oxide. Suitable molecular sieve zeolites are those having pore diameters of at least 5 Å (0.5 nm) and containing exchangeable cations, for example, faujasite crystalline aluminosilicates, mordenite crystalline aluminosilicates, ZSM crystalline aluminosilicates, and AMS crystalline metallosilicates. 
     There are also disclosed processes for the hydrodenitrogenation and hydrocracking of a hydrocarbon stream containing a substantial amount of nitrogen compounds, which processes comprise contacting said stream under suitable conditions and in the presence of hydrogen with the aforesaid catalyst.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation-in-part application of co-pendingapplication U.S. Ser. No. 200,536, which was filed in the U.S. Patentand Trademark Office on Oct. 24, 1980.

U.S. Ser. No. 200,536 was filed concurrently with and is co-pending withU.S. Ser. No. 200,544, now abandoned, which discloses the hydrotreatingof nitrogen-containing feeds in the presence of a catalyst comprising ahydrogenation component comprising chromium, molybdenum, and at leastone metal of Group VIII and an alumina-silica support, which supportcontains silica in an amount within the range of about 10 wt% to about50 wt%, based upon the weight of the catalyst support.

BACKGROUND OF THE INVENTION

This invention is related to the catalytic hydrotreatment of a feedstockcontaining large concentrations of nitrogen compounds in the presence ofhydrogen to hydrocrack said feedstock and to remove nitrogen compoundstherefrom.

In U.S. Pat. No. 2,971,904, Gladrow, et al., disclose various processes,such as hydroforming, cracking, and hydroisomerization, which processesemploy a catalyst comprising a hydrogenation component, such asmolybdenum, chromium, tungsten, vanadium, platinum group metals, nickel,copper, cobalt, cobalt molybdate, and mixtures thereof, deposited upon azeolitic crystalline aluminosilicate molecular sieve.

In U.S. Pat. No. 3,236,761, Rabo, et al., consider processes forcracking, hydrocracking, polymerization, alkylation, dealkylation,reforming, and isomerization of hydrocarbons, which processes employ azeolitic molecular sieve catalyst. The zeolitic molecular sieve has lessthan 90 percent of the aluminum atoms associated with cations and isidentified as a decationized zeolitic molecular sieve. The silicondioxide to aluminum trioxide molar ratio of this molecular sieve isgreater than 3. While the preferred metals are palladium and platinum,other catalytically active metals, such as titanium, chromium,molybdenum, tungsten, rhenium, manganese, zinc, and vanadium can beintroduced into the crystalline aluminosilicate by any method.

In U.S. Pat. No. 3,236,762, Rabo, et al., disclose a process for theconversion of hydrocarbons, which process comprises contacting thehydrocarbons with a zeolitic molecular sieve having at least 40 percentof the aluminum tetrahedra satisfied by the presence of polyvalent metalcations. Metals such as palladium, platinum, titanium, chromium,molybdenum, tungsten, rhenium, manganese, zinc, and vanadium can beintroduced into the crystalline aluminosilicate by any method which willresult in dispersing the catalytically active metal. This patentdiscloses processes for isomerization, reforming, hydrocracking,alkylation, and dealkylation.

In U.S. Pat. No. 2,882,244, Milton discloses X-type crystalline zeoliticmolecular sieves.

In U.S. Pat. No. 2,962,435, Fleck, et al., disclose the improvedconversion of feedstocks that are contaminated with certain organicnitrogen compounds by employing a catalyst comprising a syntheticzeolitic metallo aluminosilicate which has been activated by partialdehydration. Such aluminosilicate has pores of at least 7 Å in diameter.Such process and catalyst are particularly useful for the catalyticcracking of hydrocarbon mixtures containing certain organic nitrogencompounds.

In U.S. Pat. No. 3,130,006, Rabo, et al., disclose a decationizedzeolitic molecular sieve having a silicon dioxide to aluminum trioxidemolar ratio greater than about 3.0 and a pore size that is sufficient toabsorb benzene, and a metal-cation-to-aluminum atomic ratio of less thanabout 0.9, less than 90 percent of the aluminum atoms being associatedwith cations. Examples of such zeolites are faujasite, Y-type, andL-type molecular sieves.

In U.S. Pat. No. 3,130,007, Breck discloses crystalline Zeolite Y. Thismolecular sieve has a silicon dioxide to aluminum trioxide molar ratiothat is greater than 3 and up to about 6.

In U.S. Pat. No. 3,013,988, Bukata, et al., disclose zeolitic molecularsieves containing at least one metal selected from the group consistingof chromium, molybdenum, and tungsten or oxides of these metals. Thecrystalline metal aluminosilicate zeolite can be a Zeolite X, Zeolite Y,and faujasite.

In U.S. Pat. No. 3,140,322, Frilette, et al., disclose a process forselectively conducting an organic chemical reaction, which processemploys a crystalline aluminosilicate zeolite molecular sieve materialof the X-type and A-type. The sodium or calcium ions of the zeolite maybe replaced by such metal ions as lithium, magnesium, potassium, silver,strontium, nickel, cobalt, iron, zinc, mercury, cadmium, gold, scandium,titanium, vanadium, chromium, manganese, tungsten, yttrium, zirconium,niobium, molybdenum, hafnium, tantalum, aluminum, and other ions, suchas ammonium and hydrogen ions. This patent teaches general methods forconverting chemical substances catalytically under conditions whichimpose selectivity of reaction paths by virtue of providingcatalytically active sites within crystalline substances, theinterstitial dimensions of which will selectively pass or reject certainmolecules. Examples of such reactions are dehydration of normal butanol,cracking of normal paraffins, and hydrogenation of double-bond oraromatic bond units.

In United Kingdom Patent Specification No. 731,638, there is disclosed amethod for preparing a reforming catalyst, which catalyst consists of amajor proportion of alumina (50 wt% to 89 wt%), a minor proportion ofchromia (10 wt% to 30 wt%), and a minor proportion of molybdena (1 wt%to 20 wt%). This United Kingdom patent teaches that such a catalystprovides improved selectivity, activity, and stability for the reformingof hydrocarbon streams.

In U.S. Pat. No. 4,188,284, Quick, et al., disclose a process for thehydrotreating of a heavy hydrocarbon stream wherein said stream iscontacted under suitable conditions and in the presence of hydrogen witha catalyst comprising a hydrogenating component consisting essentiallyof (1) molybdenum and chromium, (2) their oxides, (3) their sulfides, or(4) mixtures thereof on a large-pore, catalytically active alumina, saidmolybdenum being present within the range of about 5 wt% to about 15wt%, calculated as MoO₃ and based upon the total catalyst weight, saidchromium being present in an amount within the range of about 5 wt% toabout 20 wt%, calculated as Cr₂ O₃ and based upon the total catalystweight, and said catalyst having a pore volume within the range of about0.4 cc/gm to about 0.8 cc/gm, a surface area within the range of about150 m² /gm to about 300 m² /gm, and an average pore diameter within therange of about 100 Å to about 200 Å.

In U.S. Pat. No. 4,181,602, Quick, et al., disclose a process for thehydrotreating of a heavy hydrocarbon stream wherein said stream iscontacted under suitable conditions and in the presence of hydrogen witha catalyst comprising (1) the metals of molybdenum, chromium, andcobalt, (2) their oxides, (3) their sulfides, or (4) mixtures thereof ona large-pore, catalytically active alumina, said molybdenum beingpresent in an amount within the range of about 5 wt% to about 15 wt%,calculated as MoO₃ and based upon the total catalyst weight, saidchromium being present in an amount within the range of about 5 wt% toabout 20 wt%, calculated as Cr₂ O₃ and based upon the total catalystweight, said cobalt being present in an amount within the range of about0.1 wt% to about 5 wt%, calculated as CoO and based upon the totalcatalyst weight, and said catalyst possessing a pore volume within therange of about 0.4 cc/gm to about 0.8 cc/gm, a surface area within therange of about 150 m² /gm to about 300 m² /gm, and an average porediameter within the range of about 100 Å to about 200 Å.

In U.S. Pat. No. 4,191,635, Quick, et al., disclose a process for thehydrotreating and cracking of a heavy hydrocarbon stream containingmetals, asphaltenes, nitrogen compounds, and sulfur compounds, whichprocess comprises hydrotreating the stream in the presence of a catalystcomprising molybdenum and chromium, and optionally cobalt, on alarge-pore alumina to provide a hydrotreated product and catalyticallycracking at least a portion of the hydrotreated product.

In U.S. Pat. No. 4,153,540, Gorring, et al., disclose a process for thetreating of shale oil, wherein the shale oil is first hydrotreated toconvert sulfur, nitrogen, and oxygen derivatives to hydrogen sulfides,ammonia, and water and the hydrotreated material is hydrocracked over acatalyst comprising a zeolite such as HZSM-5 and ahydrogenation/dehydrogenation metal.

In U.S. Pat. No. 4,224,144, Hensley, Jr., et al., disclose thehydrotreating of a hydrocarbon stream to remove nitrogen and sulfurtherefrom, which stream is selected from petroleum hydrocarbondistillates, tar sands distillates, and shale oil. The catalyst employedin this hydrotreating process is a catalyst comprising a hydrogenationcomponent comprising chromium, molybdenum, and a Group VIII metaldeposited upon a porous refractory inorganic oxide support or carrier,such as alumina, silica-alumina, silica, magnesia, zirconia, and similarmaterials.

Now there has been found a catalyst which can be used tohydrodenitrogenate and hydrocrack successfully petroleum hydrocarbondistillates, liquids obtained from coal, liquids obtained from tarsands, and shale oil.

SUMMARY OF THE INVENTION

There is provided a catalytic composition and a process for thehydrodenitrogenation and hydrocracking of a hydrocarbon streamcontaining a substantial amount of nitrogen compounds, which processemploys the aforesaid catalytic composition.

The catalyst comprises a hydrogenation component, a porous refractoryinorganic oxide, and a crystalline molecular sieve zeolite, saidhydrogenation component comprising chromium, molybdenum, and at leastone Group VIII metal. The hydrogenation component can be deposed upon asupport of the molecular sieve zeolite and refractory inorganic oxide.Alternatively, the hydrogenation component can be deposed upon therefractory inorganic oxide, which is physically mixed with the molecularsieve zeolite. A suitable molecular sieve zeolite is one havingexchangeable cations and pore openings that are at least 5 Angstromunits (Å) (0.5 nm). Consequently, a suitable molecular sieve material isa member selected from the group consisting of a faujasite-typecrystalline aluminosilicate, a mordenite-type crystallinealuminosilicate, a ZSM-type crystalline aluminosilicate, and an AMS-typecrystalline metallosilicate. The molecular sieve zeolite is present inan amount within the range of about 5 wt% to about 90 wt%, based uponthe weight of said support, and the metals of said hydrogenationcomponent are present in the elemental form, as oxides, as sulfides, oras mixtures thereof. Typical examples of suitable molecular sieves areultrastable, large-pore crystalline aluminosilicate material, acrystalline Y-type aluminosilicate, a ZSM-5 crystalline aluminosilicate,and an AMS-1B crystalline borosilicate.

There is provided also a process which comprises contacting a heavyhydrocarbon stream containing a substantial amount of nitrogen compoundsunder suitable conditions and in the presence of hydrogen with theaforesaid catalyst to produce motor fuel components, heater oilcomponents, and a feedstock for a catalytic cracking unit.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to a novel catalyst and to a novelprocess employing that catalyst, which process is a process for thehydrodenitrogenation and hydrocracking of a hydrocarbon streamcontaining a substantial amount of nitrogen compounds.

The catalyst and the process of the present invention can be usedconveniently to treat a hydrocarbon stream containing a substantialamount of nitrogen compounds. The phrase "containing a substantialamount of nitrogen compounds" refers to an amount that will result in atleast 0.2 wt% nitrogen in the particular stream. Such hydrocarbonstreams are selected from the group consisting of petroleum hydrocarbondistillates, liquids derived from coal, liquids derived from tar sands,and shale oil. Typical examples of petroleum hydrocarbon distillates arelight virgin gas oils, heavy vacuum gas oils, heavy coker gas oils, andfull range gas oils. Hydrocarbon streams derived from oil shale can be awhole shale oil or any fraction thereof. Such feedstocks often containfrom about 0.2 wt% nitrogen to about 3.0 wt% nitrogen, or more.

Such hydrocarbon feeds contain substantial quantities of nitrogencompounds and such nitrogen compounds must be removed therefrom beforethe hydrocarbons can be used for fuels. One way of removing suchnitrogen compounds comprises the hydrodenitrogenating of the hydrocarbonstream in the presence of hydrogen, under suitable conditions, and inthe presence of a suitable catalyst.

While the catalyst and process of the present invention can be used totreat a hydrocarbon stream containing a substantial amount of nitrogencompounds, they can be used also to treat a hydrocarbon stream thatcontains less than 0.2 wt% nitrogen.

Broadly, there is provided a catalyst which comprises a hydrogenationcomponent comprising chromium, molybdenum, and at least one Group VIIImetal, a crystalline molecular sieve zeolite having a pore diameter ofat least 5 Å (0.5 nm) and containing exchangeable cations, and a porousrefractory inorganic oxide, the metals of said hydrogenation componentbeing present in the elemental form, as oxides, as sulfides, or mixturesthereof. In one embodiment, there is provided a catalyst which comprisesa hydrogenation component comprising chromium, molybdenum, and at leastone Group VIII metal deposed upon a porous support comprising acrystalline molecular sieve zeolite having a pore diameter of at least 5Å (0.5 nm) and containing exchangeable cations suspended in anddistributed throughout a matrix of a refractory inorganic oxide, themetals of said hydrogenation component being present in the elementalform, as oxides, as sulfides, or mixtures thereof. In anotherembodiment, there is provided a catalyst which comprises a hydrogenationcomponent comprising chromium, molybdenum, and at least one Group VIIImetal deposed upon a refractory inorganic oxide that is intimatelyadmixed in a physical particulate mixture with a crystalline molecularsieve zeolite having a pore diameter of at least 5 Å (0.5 nm) andcontaining exchangeable cations, the metals of said hydrogenationcomponent being present in the elemental form, as oxides, as sulfides,or mixtures thereof.

More particularly, there is provided a catalyst which comprises ahydrogenation component comprising chromium, molybdenum, and at leastone Group VIII metal deposed upon a porous support comprising acrystalline molecular sieve zeolite selected from the group consistingof a faujasite-type crystalline aluminosilicate, a mordenite-typecrystalline aluminosilicate, a ZSM-type crystalline aluminosilicate, andan AMS-type crystalline metallosilicate suspended in and distributedthroughout a matrix of a refractory inorganic oxide support material,the metals of said hydrogenation component being present in theelemental form, as oxides, as sulfides, or mixtures thereof. Inaddition, there is provided a catalyst which comprises a hydrogenationcomponent comprising chromium, molybdenum, and at least one Group VIIImetal deposed upon a porous support comprising a crystalline molecularsieve zeolite selected from the group consisting of ultrastable,large-pore crystalline aluminosilicate material, a rare earthmetal-exchanged Y-type aluminosilicate, a ZSM-5 crystallinealuminosilicate, and an AMS-1B crystalline borosilicate suspended in anddistributed throughout a matrix of a refractory inorganic oxide supportmaterial, the metals of said hydrogenation component being present inthe elemental form, as oxides, as sulfides, or mixtures thereof.

There is also provided a process for the hydrodenitrogenation andhydrocracking of a hydrocarbon stream containing a substantial amount ofnitrogen compounds, which process comprises contacting said stream in areaction zone under suitable conditions and in the presence of hydrogenwith a catalyst comprising a hydrogenation component comprisingchromium, molybdenum, and at least one Group VIII metal, a crystallinemolecular sieve zeolite having a pore diameter of at least 5 Å (0.5 nm)and containing exchangeable cations, and a porous refractory inorganicoxide, the metals of said hydrogenation component being present in theelemental form, as oxides, as sulfides, or mixtures thereof. In oneembodiment, there is provided a process for the hydrodenitrogenation andhydrocracking of a hydrocarbon stream containing a substantial amount ofnitrogen compounds, which process comprises contacting said stream in areaction zone under suitable conditions and in the presence of hydrogenwith a catalyst comprising a hydrogenation component comprisingchromium, molybdenum, and at least one Group VIII metal deposed upon aporous support comprising a crystalline molecular sieve zeolite having apore diameter of at least 5 Å (0.5 nm) and containing exchangeablecations suspended in and distributed throughout a matrix of a refractoryinorganic oxide support material, the metals of said hydrogenationcomponent being present in the elemental form, as oxides, as sulfides,or mixtures thereof. In another embodiment, there is provided a processfor the hydrodenitrogenation and hydrocracking of a hydrocarbon streamcontaining a substantial amount of nitrogen compounds, which processcomprises contacting said stream in a reaction zone under suitableconditions and in the presence of hydrogen with a catalyst comprising ahydrogenation component comprising chromium, molybdenum, and at leastone Group VIII metal deposed upon a refractory inorganic oxide that isintimately admixed in a physical particulate mixture with a crystallinemolecular sieve zeolite having a pore diameter of at least 5 Å (0.5 nm)and containing exchangeable cations, the metals of said hydrogenationcomponent being present in the elemental form, as oxides, as sulfides,or mixtures thereof.

More particularly, there is provided a process for thehydrodenitrogenation and hydrocracking of a hydrocarbon streamcontaining a substantial amount of nitrogen compounds, which processcomprises contacting said stream in a reaction zone under suitableconditions and in the presence of hydrogen with a catalyst comprising ahydrogenation component comprising chromium, molybdenum, and at leastone Group VIII metal deposed upon a porous support comprising acrystalline molecular sieve zeolite selected from the group consistingof a faujasite-type crystalline aluminosilicate, a mordenite-typecrystalline aluminosilicate, a ZSM-type crystalline aluminosilicate, andan AMS-type crystalline metallosilicate suspended in and distributedthroughout a matrix of a refractory inorganic oxide support material,the metals of said hydrogenation component being present in theelemental form, as oxides, as sulfides, or mixtures thereof. Inaddition, there is provided a process for the hydrodenitrogenation andhydrocracking of a hydrocarbon stream containing a substantial amount ofnitrogen compounds, which process comprises contacting said stream in areaction zone under suitable conditions and in the presence of hydrogenwith a catalyst comprising a hydrogenation component comprisingchromium, molybdenum, and at least one Group VIII metal deposed upon aporous support comprising a crystalline molecular sieve zeolite selectedfrom the group consisting of ultrastable, large-pore crystallinealuminosilicate material, a crystalline Y-type aluminosilicate, a rareearth metal-exchanged crystalline Y-type aluminosilicate, a ZSM-5crystalline aluminosilicate, and an AMS-1B crystalline borosilicatesuspended in and distributed throughout a matrix of a refractoryinorganic oxide support material, the metals of said hydrogenationcomponent being present in the elemental form, as oxides, as sulfides,or mixtures thereof.

In addition, there is provided a process for the hydrodenitrogenationand hydrocracking of a hydrocarbon stream comprising whole shale oil orany fraction thereof to produce jet fuel components, which processcomprises contacting said stream in a reaction zone under suitableconditions and in the presence of hydrogen with a catalyst comprising ahydrogenation component comprising chromium, molybdenum, and at leastone Group VIII metal, a crystalline molecular sieve zeolite having apore diameter of at least 5 Å (0.5 nm) and containing exchangeablecations, and a porous refractory inorganic oxide, the metals of saidhydrogenation component being present in the elemental form, as oxides,as sulfides, or mixtures thereof. In one embodiment, there is provided aprocess for the hydrodenitrogenation and hydrocracking of a hydrocarbonstream comprising whole shale oil or any fraction thereof to produce jetfuel components, which process comprises contacting said stream in areaction zone under suitable conditions and in the presence of hydrogenwith a catalyst comprising a hydrogenation component comprisingchromium, molybdenum, and at least one Group VIII metal deposed upon aporous support comprising a crystalline molecular sieve zeolite having apore diameter of at least 5 Å (0.5 nm) and containing exchangeablecations suspended in and distributed throughout a matrix of a refractoryinorganic oxide, the metals of said hydrogenation component beingpresent in the elemental form, as oxides, as sulfides, or mixturesthereof. In another embodiment, there is provided a process for thehydrodenitrogenation and hydrocracking of a hydrocarbon streamcomprising whole shale oil or any fraction thereof to produce jet fuelcomponents, which process comprises contacting said stream in a reactionzone under suitable conditions and in the presence of hydrogen with acatalyst comprising a hydrogenation component comprising chromium,molydenum, and at least one Group VIII metal deposed upon a refractoryinorganic oxide that is intimately admixed in a physical particulatemixture with a crystalline molecular sieve zeolite having a porediameter of at least 5 Å (0.5 nm) and containing exchangeable cations,the metals of said hydrogenation component being present in theelemental form, as oxides, as sulfides, or mixtures thereof.

More particularly, there is provided a process for thehydrodenitrogenation and hydrocracking of a hydrocarbon streamcomprising whole shale oil or any fraction thereof to produce jet fuelcomponents, which process comprises contacting said stream in a reactionzone under suitable conditions and in the presence of hydrogen with acatalyst comprising a hydrogenation component comprising chromium,molybdenum, and at least one Group VIII metal deposed upon a supportcomprising a crystalline molecular sieve zeolite selected from the groupconsisting of a faujasite-type crystalline aluminosilicate, amordenite-type crystalline aluminosilicate, a ZSM-type crystallinealuminosilicate, and an AMS-type crystalline metallosilicate suspendedin and distributed throughout a matrix of a refractory inorganic oxidesupport material, the metals of said hydrogenation component beingpresent in the elemental form, as oxides, as sulfides, or mixturesthereof. In addition, there is provided a process for thehydrodenitrogenation and hydrocracking of a hydrocarbon streamcomprising whole shale oil or any fraction thereof to produce jet fuelcomponents, which process comprises contacting said stream in a reactionzone under suitable conditions and in the presence of hydrogen with acatalyst comprising a hydrogenation component comprising chromium,molybdenum, and at least one Group VIII metal deposed upon a poroussupport comprising a crystalline molecular sieve zeolite selected fromthe grouup consisting of ultrastable, large-pore crystallinealuminosilicate material, a crystalline Y-type aluminosilicate, a rareearth metal-exchanged crystalline Y-type aluminosilicate, a ZSM-5crystalline aluminosilicate, and an AMS-1B crystalline borosilicatesuspended in and distributed throughout a matrix of a refractoryinorganic oxide support material, the metals of said hydrogenationcomponent being present in the elemental form, as oxides, as sulfides,or mixtures thereof.

The catalyst of the present invention contains a hydrogenation componentdeposed or deposited upon a porous support comprising a molecular sievezeolite and a refractory inorganic oxide or, alternatively, upon therefractory inorganic oxide. This hydrogenation component compriseschromium, molybdenum, and at least one Group VIII metal from thePeriodic Table of Elements. The Periodic Table of Elements referred toherein is the table found on page 628 of WEBSTER'S SEVENTH NEWCOLLEGIATE DICTIONARY, G. & C. Merriam Company, Springfield, Mass.,U.S.A. (1963). The various metals of the hydrogenation component can bepresent in the elemental form, as oxides, as sulfides, or as mixturesthereof. The Group VIII metal is advantageously a non-noble metal and ispreferably nickel or cobalt.

The catalyst contains the metal of Group VIII in an amount which fallswithin the range of about 0.5 wt% to about 10 wt%, calculated as theoxide of the metal, the molybdenum is present in an amount that fallswithin the range of about 5 wt% to about 25 wt%, calculated as MoO₃, andthe chromium in an amount that falls within the range of about 3 wt% toabout 15 wt%, calculated as Cr₂ O₃, each amount being based upon theweight of the catalyst. Preferably, the catalyst should contain theGroup VIII metal, preferably cobalt or nickel, in an amount within therange of about 1 wt% to about 5 wt%, calculated as the oxide of themetal, molybdenum in an amount within the range of about 12 wt% to about18 wt%, calculated as MoO₃, and chromium in an amount within the rangeof about 7 wt% to about 12 wt%, calculated as Cr₂ O₃, each amount beingbased upon the total weight of the catalyst.

An essential component of the support material of the catalyst of thepresent invention is a crystalline molecular sieve zeolite having a porediameter of at least 5 Å (0.5 nm) and containing exchangeable cations.Such molecular sieve zeolite can be selected from the group consistingof a faujasite-type crystalline aluminosilicate, a mordenite-typecrystalline aluminosilicate, a ZSM-type crystalline aluminosilicate, andan AMS-type crystalline metallosilicate. Examples of a faujasite-typecrystalline aluminosilicate are high- and low-alkali metal Y-typecrystalline aluminosilicates, metal-exchanged X-type and Y-typecrystalline aluminosilicates, and ultrastable, large-pore crystallinealuminosilicate material. Zeolon is an example of a mordenite-typecrystalline aluminosilicate. An example of a ZSM-type crystallinealuminosilicate is ZSM-5 crystalline aluminosilicate. AMS-1B crystallineborosilicate is an example of an AMS-type crystalline metallosilicate.One or more of these molecular sieves are suspended in and distributedthroughout a matrix of a refractory inorganic oxide material. Themolecular sieve component is present in an amount within the range ofabout 5 wt% to about 90 wt%, preferably within the range of about 20 wt%to about 50 wt%, based upon the weight of the support of the catalyst,which support is made up of the molecular sieve material and therefractory inorganic oxide. Such concentrations of zeolite will providesuitable catalysts for upgrading feeds containing substantial amounts ofnitrogen.

Ultrastable, large-pore crystalline aluminosilicate material isrepresented by Z-14US zeolites which are described in U.S. Pat. Nos.3,293,192 and 3,449,070. Each of these patents is incorporated byreference herein and made a part hereof. By large-pore material is meanta material that has pores which are sufficiently large to permit thepassage thereinto of benzene molecules and larger molecules and thepassage therefrom of reaction products. For use in petroleum hydrocarbonconversion processes, it is often preferred to employ a large-poremolecular sieve material having a pore size of at least 5 Å (0.5 nm) to10 Å (1 nm).

The ultrastable, large-pore crystalline aluminosilicate material isstable to exposure to elevated temperatures. This stability to elevatedtemperatures is discussed in the aforementioned U.S. Pat. Nos. 3,293,192and 3,449,070. It may be demonstrated by a surface area measurementafter calcination at 1,725° F. In addition, the ultrastable, large-porecrystalline aluminosilicate material exhibits extremely good stabilitytoward wetting, which is defined as the ability of a particularaluminosilicate material to retain surface area or nitrogen-adsorptioncapacity after contact with water or water vapor. A sodium-form of theultrastable, large-pore crystalline aluminosilicate material (about 2.15wt% sodium) was shown to have a loss in nitrogen-adsorption capacitythat is less than 2% per wetting, when tested for stability to wettingby subjecting the material to a number of consecutive cycles, each cycleconsisting of a wetting and a drying.

The ultrastable, large-pore crystalline aluminosilicate material that ispreferred for the catalytic composition of this invention exhibits acubic unit cell dimension and hydroxyl infrared bands that distinguishit from other aluminosilicate materials. The cubic unit cell dimensionof the preferred ultrastable, large-pore crystalline aluminosilicate iswithin the range of about 24.20 Angstrom units (Å) to about 24.55 Å. Thehydroxyl infrared bands obtained with the preferred ultrastable,large-pore crystalline aluminosilicate material are a band near 3,745cm⁻¹ (3,745±5 cm⁻¹), a band near 3,695 cm⁻¹ (3,690±10 cm⁻¹), and a bandnear 3,625 cm⁻¹ (3,610±15 cm⁻¹). The band near 3,745 cm⁻¹ may be foundon many of the hydrogen-form and decationized aluminosilicate materials,but the band near 3,695 cm⁻¹ and the band near 3,625 cm⁻¹ arecharacteristic of the preferred ultrastable, large-pore crystallinealuminosilicate material that is used in the catalyst of the presentinvention.

The ultrastable, large-pore crystalline aluminosilicate material ischaracterized also by an alkaline metal content of less than 1%.

Other examples of crystalline molecular sieve zeolites that are suitablefor the catalyst of the present invention are a high-sodium Y-typecrystalline aluminosilicate such as the sodium-Y molecular sievedesignated Catalyst Base 30-200 and obtained from the Linde Division ofUnion Carbide Corporation and a low-sodium Y-type molecular sievedesignated as low-soda Diuturnal-Y-33-200 and obtained from the LindeDivision of Union Carbide Corporation.

Another example of a crystalline molecular sieve zeolite that can beemployed in the catalytic composition of the present invention is ametal-exchanged Y-type molecular sieve. Y-type zeolitic molecular sievesare discussed in U.S. Pat. No. 3,130,007. The metal-exchanged Y-typemolecular sieve can be prepared by replacing the original cationassociated with the molecular sieve by a wide variety of other cationsaccording to techniques that are known in the art. Ion exchangetechniques have been disclosed in many patents, several of which areU.S. Pat. Nos. 3,140,249, 3,140,251, and 3,140,253. Specifically, amixture of rare earth metals can be exchanged into a Y-type zeoliticmolecular sieve and such rare earth metal-exchanged Y-type molecularsieve can be employed suitably in the catalytic composition of thepresent invention. Specific examples of suitable rare earth metals arecerium, lanthanum, and praseodymium.

Another zeolitic molecular sieve material that is used in the catalyticcomposition of the present invention is ZSM-5 crystalline zeoliticmolecular sieves. Descriptions of the ZSM-5 composition and its methodof preparation are presented by Argauer, et al., in U.S. Pat. No.3,702,886. This patent is incorporated by reference herein and made apart hereof.

An additional molecular sieve that can be used in the catalyticcomposition of the present invention is AMS-1B crystalline borosilicate,which is described in U.S. Pat. No. 4,269,813, which patent isincorporated by reference herein and made a part hereof.

A suitable AMS-1B crystalline borosilicate is a molecular sieve materialhaving the following composition in terms of mole ratios of oxides:

    0.9±0.2M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation having a valence of n, Y is within therange of 4 to about 600, and Z is within the range of 0 to about 160,and providing an X-ray diffraction pattern comprising the followingX-ray diffraction lines and assigned strengths:

    ______________________________________                                                       Assigned                                                              d (Å)                                                                             Strength                                                       ______________________________________                                               11.2 ± 0.2                                                                         W-VS                                                                  10.0 ± 0.2                                                                         W-MS                                                                  5.97 ± 0.07                                                                        W-M                                                                   3.82 ± 0.05                                                                        VS                                                                    3.70 ± 0.05                                                                        MS                                                                    3.62 ± 0.05                                                                        M-MS                                                                  2.97 ± 0.02                                                                        W-M                                                                   1.99 ± 0.02                                                                        VW-M                                                           ______________________________________                                    

Mordenite-type crystalline aluminosilicates can be employed in thecatalyst of the present invention. Mordenite-type crystallinealuminosilicate zeolites have been discussed in patent art, e.g., byKimberlin in U.S. Pat. No. 3,247,098, by Benesi, et al., in U.S. Pat.No. 3,281,483, and by Adams, et al., in U.S. Pat. No. 3,299,153. Thoseportions of each of these patents which portions are directed tomordenite-type aluminosilicates are incorporated by reference herein andmade a part hereof. Synthetic mordenite-structure crystallinealuminosilicate zeolites, designated as Zeolon, are available from theNorton Company of Worcester, Mass., U.S.A.

The other essential component of the support material of the catalyst ofthe present invention is a high-surface area inorganic oxide support,such as alumina, silica, or a mixture of silica and alumina. Themixtures of silica and alumina can include, but not be limited to, thosecompositions which are recognized by one having ordinary skill in theart as being a component of fluid cracking catalysts. Suchsilica-alumina material contains alumina, generally, within the range ofabout 10 wt% to about 45 wt%.

A preferred high-surface area refractory inorganic oxide iscatalytically active alumina, such as gamma-alumina or eta-alumina. Suchaluminas have a surface area within the range of about 150 m² /gm toabout 350 m² /gm, or larger, a pore volume within the range of about 0.3cc/gm to about 1 cc/gm, and an average pore diameter within the range ofabout 60 Å (6 nm) to about 200 Å (20 nm).

The catalytic composition of the present invention can be prepared byfirst making a support material comprising the particular crystallinezeolitic molecular sieve and matrix of a refractory inorganic oxide,such as alumina. This is done preferably by blending finely-dividedcrystalline molecular sieve in a sol, hydrosol, or hydrogel of theinorganic oxide, adding a gelling medium such as ammonium hydroxide tothe blend with constant stirring to produce a gel, drying, pelleting orextruding, and calcining. Drying can be accomplished in static air at atemperature within the range of 80° F. (27° C.) to about 350° F. (177°C.) for a period of time within the range of about 1 hour to about 50hours. Calcination is performed conveniently by heating in air at atemperature in excess of 800° F. (427° C.) to about 1,200° F. (649° C.)for a period within the range of about 0.5 hour to about 16 hours.

An alternative method for preparing the catalyst support comprisesphysically mixing finely-divided particles of the appropriate molecularsieve zeolite with finely-divided particles of the refractory inorganicoxide, thoroughly blending the mechanical mixture, and subsequentlypelleting or extruding the blended mixture into appropriately-sizedparticles. If the hydrogenation component is to be solely upon therefractory inorganic oxide portion of the support material, thefinely-divided particles of the appropriate molecular sieve zeolite canbe physically admixed with finely-divided particles of the impregnatedrefractory inorganic oxide, and the mechanical mixture can be blendedand subsequently pelleted or extruded into appropriately-sizedparticles.

The catalyst of the present invention can be used conveniently in afixed bed in the form of pellets, spheres, or extrudates. It iscontemplated further that the catalyst can be present as other shapes,such as a clover leaf, cross shape, or C shape, as disclosed byHoekstra, et al., in U.S. Pat. Nos. 3,674,680 and 3,764,565.

The hydrogenation component can then be incorporated onto the resultantsupport material by impregnation of the support with one or moresolutions of heat-decomposable metal compounds, drying, and calcining asdescribed hereinabove. If impregnation is to be performed with more thanone solution, it is preferred that the solution containing the compoundof chromium be applied first. However, it is to be understood that themetals can be applied in any order. In the case when the hydrogenationcomponent is to be deposed upon the refractory inorganic oxide, one ormore solutions of heat-decomposable metal compounds are employed toimpregnate the particular refractory inorganic oxide with the variousmetals. Such impregnation can be followed by drying and calcining asdescribed hereinabove. The impregnated refractory inorganic oxidematerial in a finely-divided form can then be physically admixed withappropriately-sized particles of the selected molecular sieve zeolite.

The catalyst of the present invention is characterized by the followingapparent pore size distribution, as would be obtained by a Digisorb 2500instrument employing nitrogen desorption techniques: 30% to 55% of thetotal pore volume in pores having diameters less than 50 Å (5 nm); 30%to 60% of the total pore volume in pores having diameters within therange of 50 Å (5 nm) to 100 Å (10 nm); and less than 25% of the totalpore volume in pores having diameters greater than 100 Å (10 nm). Theterm "apparent pore size distribution" is used since the large range ofcatalyst-support-composition values makes it very difficult to fixranges of values for the pore size distribution.

An advantage of the catalyst of the present invention is itshigh-temperature stability, i.e., its ability to perform satisfactorilyat high temperatures over an extended period of time. The hightemperature is an ideal condition since it enables ammonia to bedesorbed and permits hydrocracking to occur in the presence of ammonia.This ideal condition of high temperature does not appear to effectdeleteriously the performance of the catalyst. The chromium in thehydrogenation component of the catalyst provides the high temperaturestability. The combination of a Group VIII metal and molybdenum affordsan active component for hydrogenation, denitrogenation anddesulfurization. The presence of a molecular sieve zeolite in thecatalyst provides an acidic component which promotes denitrogenation andcracking. The presence of the refractory inorganic oxide affords asuitable high-surface area for the active component of the catalyst.

The acidity of the catalyst of the present invention can be enhanced bythe addition of a halogen, for example, fluorine or chlorine.

Prior to use in the process of the present invention, the catalyst issubjected to a sulfiding pretreatment. This sulfiding pretreatment isnecessary because the metal constituents of the hydrogenation componentshould be in a partially-reduced state. The sulfiding will provide suchpartially-reduced metals, but will not reduce the metals completely tothe elemental form, which form is inactive.

A convenient sulfiding pretreatment comprises heating the catalyst to atemperature within the range of about 250° F. (121° C.) to about 350° F.(177° C.), passing a gas mixture of hydrogen sulfide in hydrogen overand through the catalyst at a variable pressure for a period of about0.5 hour to about 2 hours, raising the temperature to a value within therange of about 350° F. (177° C.) to about 450° F. (232° C.), continuingto pass the gas mixture at this latter temperature over and through thecatalyst for an additional period of about 0.5 hour to about 2 hours,raising the temperature to a value of about 650° F. (343° C.) to about750° F. (399° C.), and continuing to pass the hydrogen sulfide-hydrogengas mixture through the catalyst for an additional period of about 0.5hour to about 2 hours. Suitably, sufficient gas should be employed toprovide about 110% of the stoichiometric amount of hydrogen sulfideneeded to sulfide the metals of the hydrogenation component. Theconcentration of hydrogen sulfide in the gas is not critical.Subsequently, hydrogen-containing gas is introduced into the reactor andpermitted to flow through the catalyst at operating pressure. A suitableflow rate for the hydrogen-containing gas is the hydrogen addition rateprovided hereinbelow. The hydrocarbon feed to be treated by the processcan then be introduced into the reactor.

While the above sulfiding pretreatment is a convenient way ofpretreating the catalyst, other suitable methods known to those skilledin the art can be employed. For example, carbon disulfide can be addedto the zone containing the catalyst or a light hydrocarbon oilcontaining sulfur can be passed over the catalyst for a time that issufficient to provide the appropriate metal sulfides on the catalyst.

The operating conditions for the process of the present inventioncomprise a temperature within the range of about 700° F. (371° C.) toabout 800° F. (427° C.), a hydrogen partial pressure within the range ofabout 1,000 psi (6,890 kPa) to about 2,500 psi (17,225 kPa), a liquidhourly space velocity (LHSV) within the range of about 0.1 volume ofhydrocarbon per hour per volume of catalyst to about 5 volumes ofhydrocarbon per hour per volume of catalyst, a hydrogen addition rate orhydrogen recycle rate within the range of about 2,000 standard cubicfeet of hydrogen per barrel of hydrocarbon (SCFB) (359 m³ /m³) to about20,000 SCFB (3,596 m³ /m³), and a hydrogen-to-hydrocarbon molar ratiowithin the range of about 3 moles of hydrogen per mole of hydrocarbon toabout 60 moles of hydrogen per mole of hydrocarbon. Preferably, theconditions comprise a temperature within the range of about 740° F.(393° C.) to about 790° F. (416° C.), a hydrogen partial pressure withinthe range of about 1,600 psi (11,024 kPa) to about 2,000 psi (13,780kPa), an LHSV within the range of about 0.3 volume of hydrocarbon perhour per volume of catalyst to about 2 volumes of hydrocarbon per hourper volume of catalyst, a hydrogen addition rate or hydrogen recyclerate within the range of about 6,000 SCFB (1,079 m³ /m³) to about 14,000SCFB (2,517 m³ /m³), and a hydrogen-to-hydrocarbon molar ratio withinthe range of about 10 moles of hydrogen per mole of hydrocarbon to about30 moles of hydrogen per mole of hydrocarbon.

Since some of the feedstocks that can be treated by the process of thepresent invention will contain arsenic and other metals that aredetrimental to the catalyst of the process of the present invention, aguard chamber can appropriately precede the reaction zone of the processof the present invention. This guard chamber can contain a porousrefractory inorganic oxide or absorbent, such as a cheap or usedcatalyst. Such material should remove from the feedstock and retainefficiently such deleterious metals.

The following specific examples are being presented in order tofacilitate the understanding of the present invention and are presentedfor the purposes of illustration only and are not intended to limit thescope of the present invention.

Seven catalysts were prepared and tested for their ability tohydrodenitrogenate and hydrocrack a whole shale oil that had beenobtained from in situ retorting of oil shale by the Occidental PetroleumCorporation. Each of the seven catalysts and the tests of thoseparticular catalysts are presented in one of the following Examples Ithrough VII.

EXAMPLE I

A catalyst, identified hereinafter as Catalyst A, was prepared.

A 147-gram portion of Aero 100A alumina, in the form of 1/16-inchextrudates, obtained from the American Cyanamid Company was calcined ata temperature of 1,000° F. (538° C.) for at least one hour. The calcinedextrudates were then impregnated with a solution that had been preparedby dissolving 33.2 grams of (NH₄)₂ Cr₂ O₇ in 145 milliliters ofdistilled water. After standing for a short time, the impregnatedmaterial was dried in an oven under a vacuum at a temperature of about212° F. (100° C.) overnight (approximately 16 hours). The resultingdried material was then calcined in static air at a temperature of1,000° F. (538° C.) for 3 hours. The resulting material was thenimpregnated with a solution that had been prepared by dissolving 11.65grams of Co(NO₃)₂.6H₂ O and 36.8 grams of (NH₄)₆ Mo₇ O₂₄.4H₂ O insufficient distilled water to obtain 120 milliliters of solution. Thesolid material and solution were permitted to stand for approximately 1hour and then the solid material was placed in an oven under a vacuumand heated at a temperature of 212° F. (100° C.) for 2 hours andcalcined subsequently overnight (approximately 16 hours) at atemperature of 1,000° F. (538° C.).

The calcined material was then ground and sized to a 14/20-meshmaterial, i.e., material that would pass through a 14-mesh screen(Tyler) but be retained upon a 20-mesh screen (Tyler). This catalyst,identified hereinafter as Catalyst A, was prepared to contain 1.5 wt%CoO, 10 wt% Cr₂ O₃, and 15 wt% MoO₃ on an alumina support.

Catalyst A was tested in an automated hydrotreating pilot plant. Thisbench-scale test unit had automatic controls for pressure, flow ofreactants, and temperature. The reactor was made from 3/8-inch-insidediameter, stainless steel, heavy-walled tubing. A 1/8-inch-outsidediameter thermowell extended up through the center of the reactor. Thereactor was heated by an electrically-heated steel block. Thehydrocarbon feedstock was fed to the unit by means of a Ruska pump, apositive-displacement pump.

Catalyst A was loaded into a vertical reactor from the bottom up. The14/20-mesh material was supported on 8/10-mesh alundum particles, i.e.,particles that would pass through an 8-mesh screen (Tyler), but beretained upon a 10-mesh screen (Tyler). Approximately 20 cubiccentimeters of catalyst were employed as the catalyst bed in this test,as well as in each of the tests discussed hereinafter, the amount beingthat required to provide a LHSV of 0.5 cubic centimeter of hydrocarbonper hour per cubic centimeter of catalyst. This amount of catalystprovided a length of catalyst bed of about 10 inches to about 12 inches.A layer of 8/10-mesh alundum particles was placed over the catalyst tofill the top part of the reactor. The catalyst was located in theannular space between the thermowell and the internal wall of the3/8-inch-inside diameter reactor.

After the catalyst was loaded into the reactor, it was subjected to thefollowing sulfiding pretreatment. The temperature of the catalyst bedwas raised to about 300° F. (149° C.) and a gas mixture of 8% hydrogensulfide in hydrogen was passed through the catalyst bed at a variablepressure. At the end of approximately 1 hour, the temperature was raisedto about 400° F. (204° C.) and the hydrogen sulfide-containing gas waspassed over or through the catalyst for an additional hour. Then thetemperature was raised to 700° F. (371° C.) and the hydrogensulfide-hydrogen gas mixture was passed through the catalyst for anadditional hour, at which time its flow was stopped. At least onestandard cubic foot of hydrogen-hydrogen sulfide gas, and preferably atleast one standard cubic foot per hour, had been passed through thecatalyst bed. Hydrogen gas was then introduced into the reactor andallowed to flow through the catalyst bed at a pressure of 1,800 psi(12,402 kPa) and a flow rate of about 15 liters per hour. The Ruska pumpwas started, hydrocarbon bed was permitted to flow through the reactor,and the temperature of the catalyst bed was raised to the appropriatereaction temperature. Effluent from the reaction zone was passed into agas-liquid high-pressure separator, wherein the gas was separated fromthe liquid. The gas was passed through a pressure control valve and awet test meter to an appropriate vent. The liquid product was passedthrough a pressure control valve to a liquid product receiver.

In this and the following tests, the feed rate was set at about 10.3cubic centimeters per hour, a liquid hourly space velocity (LHSV) of 0.5volume of hydrocarbon per hour per volume of catalyst, and thetemperature of the catalyst bed was approximately 780° F. (416° C.). Thehydrogen addition rate was about 10,000 SCFB (1,798 m³ /m³).

The feedstock that was employed in this test, as well as in the tests inthe other examples, was a whole shale oil that had been obtained by insitu retorting by the Occidental Petroleum Corporation. The propertiesof this feed, hereinafter identified as Feed 1, are presentedhereinafter in Table I.

                  TABLE I                                                         ______________________________________                                        Properties of Feed 1                                                          ______________________________________                                        Gravity, °API      23.8                                                Carbon, wt %              84.87                                               Hydrogen, wt %            11.84                                               Nitrogen, wt %            1.32                                                Sulfur, wt %              0.64                                                Oxygen, wt %              1.33                                                Pour Point, °F.    60                                                  °C.                15.6                                                Viscosity, cst (40° C.)                                                                          32.9                                                cst (100° C.)      5.10                                                Ramsbottom Carbon, wt %   1.22                                                ASTM Distillation, °F. (°C.)                                    IBP                       290 (143)                                           5%                        404 (206)                                           30%                       566 (297)                                           60%                       744 (395)                                           % at 1,000° F. (538° C.)                                                                  87.2                                                IBP - 360° F. (182° C.), wt %                                                             1.5                                                 360° F. (182° C.)-650° F. (343° C.), wt                                     45.8                                                650° F..sup.+  (343° C..sup.+) wt %                                                       52.7                                                JP-4 Fraction, wt %       15.5                                                Contaminants, ppm                                                             Iron                      41                                                  Nickel                    10                                                  Vanadium                  about 1                                             Arsenic                   26                                                  Sodium                    about 12                                            Molybdenum                3                                                   ______________________________________                                    

For convenience, the jet fuel component is identified hereinabove inTable I and hereinafter in subsequent tables as JP-4 jet fuel boilingrange material. It is intended that such designation not limit the scopeof the process of the present invention and that the term "jet fuel" asused herein and in the claims encompass and include all types of jetfuel boiling range material.

The results obtained from the conversion of Feed No. 1 with Catalyst Ain Test No. 1 are presented hereinafter in Table II.

                                      TABLE II                                    __________________________________________________________________________    DATA FOR TEST NO. 1, CATALYST A                                               Period No.  1   2   3   4   5   6   7                                         Hours on Stream                                                                           19  43  67  91  115 139 163                                       __________________________________________________________________________    Temper-     779 --  --  780 780 780 780                                       ature, ° F.                                                            ° C. 415 --  --  416 416 416 416                                       Pressure, psig                                                                            1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                     kPa         12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                    LHSV, hr.sup.-1                                                                           0.5 0.5 0.5 0.5 0.5 0.5 0.5                                       Gravity, °API                                                                      39.9                                                                              39.0                                                                              39.1                                                                              39.1                                                                              39.0                                                                              39.2                                                                              39.2                                      Carbon, wt %                                                                              --  --  --  --  --  --  86.32                                     Hydrogen, wt %                                                                            --  --  --  --  --  --  13.65                                     Nitrogen, ppm                                                                             78  82  83  88  82  116 110                                       Sulfur, ppm 358 120 293 122 183 --  117                                       Pour Point, °F.                                                                    --  --  --  --  --  --  80                                        °C.  --  --  --  --  --  --  27                                        Viscosity, cst                                                                            --  --  --  --  --  --  3.24                                      (40° C.)                                                               IBP, °F.                                                                           --  --  --  --  --  --  5                                         °C.  --  --  --  --  --  --  -15                                       IBP - 360° F.                                                                      --  --  --  --  --  --  15.1                                      (182° C.), wt %                                                        360° F. (182° C.)-                                                          --  --  --  --  --  --  60.9                                      650° F. (343° C.),                                              wt %                                                                          650° F..sup.+  (343° C..sup.+),                                             --  --  --  --  --  24.0                                          wt %                                                                          FBP, ° F.                                                                          --  --  --  --  --  --  915                                       °C.  --  --  --  --  --  --  491                                       JP-4 Fraction,                                                                            --  --  --  --  --  --  38.1                                      wt %                                                                          Gas rate, SCFB                                                                            --  --  --  --  --  --  10.0                                      × 10.sup.3                                                              Hydrogen consumption,                                                                     --  --  --  --  --  --  1,400                                     SCFB                                                                          Wt % recovered                                                                            --  --  --  --  --  --  103.2                                     Wt % C.sub.1 -C.sub.4 on                                                                  --  --  --  --  --  --  2.8                                       Feed                                                                          __________________________________________________________________________

EXAMPLE II

A second catalyst, identified hereinafter as Catalyst B, was prepared tohave a support composed of 30 wt% ultrastable, large-porealuminosilicate material and 70 wt% alumina.

A 681-gram portion of finely-divided ultrastable, large-pore crystallinealuminosilicate material, obtained from W. R. Grace and Company, wasintroduced into 15,890 grams of a PHF-alumina hydrosol (approximately10% solids) and the resulting mixture was stirred for approximately 2hours, at which time a solution of 400 milliliters of concentratedammonium hydroxide mixed with 400 milliliters of distilled water wasadded to gel the hydrosol. The resulting gel was then dried overnight(approximately 16 hours) in static air at a temperature of 250° F. (121°C.). The dried material was then ground to pass through a 100-meshscreen (Tyler). Sufficient distilled water was added to the 100-meshmaterial to facilitate extrusion and the material was then extruded to5/64-inch extrudates and dried overnight (approximately 16 hours) at atemperature of 250° F. (121° C.). The dried extrudates were thencalcined in static air for 3 hours at a temperature of 1,000° F. (538°C.).

A 294-gram portion of the calcined material containing ultrastable,large-pore crystalline aluminosilicate material was impregnated with asolution that had been prepared by dissolving 66.4 grams of (NH₄)₂ Cr₂O₇ in 290 milliliters of distilled water. The extrudate and solutionwere mixed thoroughly and the mixture was permitted to stand overnight(approximately 16 hours). Then it was calcined at a temperature of1,000° F. (538° C.) for at least one hour. The calcined material wasthen impregnated with a solution that had been prepared by dissolving73.6 grams of (NH₄)₆ Mo₇ O₂₄.4H₂ O in 250 milliliters of distilledwater. The mixture of solution and solid was permitted to stand over theweekend (approximately 64 hours). The resulting material was thencalcined at a temperature of 1,000° F. (538° C.) for 7 hours.

A 195-gram portion of the above material was impregnated with a solutionthat had been prepared by dissolving 11.65 grams of Co(NO₃)₂ 6H₂ O in125 milliliters of distilled water. The solution and solid material weremixed and allowed to stand overnight (approximately 16 hours). Theresulting material was then calcined at a temperature of 1,000° F. (538°C.) in static air for at least one hour. The calcined material was thenground to pass through a 14-mesh screen (Tyler), but be retained upon a20-mesh screen (Tyler), i.e., to a 14/20-mesh material.

This catalyst, Catalyst B, was prepared to contain 1.5 wt% CoO, 10 wt%Cr₂ O₃, and 15 wt% MoO₃ on a support composed of 30 wt% ultrastable,large-pore crystalline aluminosilicate material and alumina.

A 20-cubic centimeter portion of Catalyst B was loaded into a reactor asdescribed hereinabove in Example I and was tested for its ability toconvert Feed 1. The results of this test, Test No. 2, are presentedhereinbelow in Table III.

                                      TABLE III                                   __________________________________________________________________________    DATA FOR TEST NO. 2, CATALYST B                                               Hours on Stream                                                                           22   46  70   94  118  142 166 190 214 238 262 286                __________________________________________________________________________    Temp., °F.                                                                         782  --  --   780 780  780 781 781 --  --  780 781                °C.  417  --  --   416 416  416 417 417 --  --  416 417                Pressure, psig                                                                            1,800                                                                              1,800                                                                             1,800                                                                              1,800                                                                             1,800                                                                              1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800              kPa         12,514                                                                             12,514                                                                            12,514                                                                             12,514                                                                            12,514                                                                             12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514             LHSV, hr.sup.-1                                                                           0.5  0.5 0.5  0.5 0.5  0.5 0.5 0.5 0.5 0.5 0.5 0.5                Gravity, °API                                                                      55.1 50.5                                                                              47.2 45.6                                                                              44.6 43.9                                                                              44.1                                                                              42.9                                                                              43.4                                                                              43.3                                                                              42.5                                                                              43.3               Carbon, wt %                                                                              --   --  --   --  85.93                                                                              --  --  --  --  --  --  86.12              Hydrogen, wt %                                                                            --   --  --   --  14.00                                                                              --  --  --  --  --  --  13.87              Nitrogen, ppm                                                                             51   13  12   7   15   2   2   5   3   3   2   14                 Sulfur, ppm 117  220 55   169 710  137 111 85  42  18  17  49                 Pour Point, °F.                                                                    --   --  --   --  30   --  --  --  --  --  --  45                 °C.  --   --  --   --  -1   --  --  --  --  --  --  7                  Viscosity, cst                                                                            --   --  --   --  1.70 --  --  --  --  --  --  2.06               (40° C.)                                                               IBP, °C.                                                                           --   --  --   --  -13  --  --  --  --  --  --  6                  IBP - 182° C., wt %                                                                --   --  --   --  29.7 --  --  --  --  --  --  24.4               182° C.-343° C.,                                                            --   --  --   --  57.3 --  --  --  --  --  --  58.0               wt %                                                                          343° C..sup.+, wt %                                                                --   --  --   --  13.0 --  --  --  --  --  --  17.6               FBP, °F.                                                                           --   --  --   --  868  --                                         °C.  --   --  --   --  465  --  --  --  --  --  --  471                JP-4 Fraction,                                                                            --   --  --   --  59.5 --  --  --  --  --  --  52.1               wt %                                                                          Gas rate, SCFB                                                                            --   --  --   --  12.0 --  --  --  --  --  --  15.0               × 10.sup.3                                                              Hydrogen consumption,                                                                     --   --  --   --  1,660                                                                              --  --  --  --  --  --  1,575              SCFB                                                                          Wt % recovered                                                                            --   --  --   --  99.5 --  --  --  --  --  --  99.6               Wt % C.sub.1 -C.sub.4 on                                                                  --   --  --   --  3.6  --  --  --  --  --  --  3.6                Feed                                                                          __________________________________________________________________________

A comparison of Catalyst B with Catalyst A shows that Catalyst Bprovided a product containing a much lower amount of nitrogen andsignificantly more naphtha and having a pour point that wassignificantly lower than that of the product obtained with Catalyst A.Therefore, Catalyst B was found to be an improved catalyst for thehydrodenitrogenation and hydrocracking of the whole shale oil feed.

EXAMPLE III

A third catalyst, hereinafter identified as Catalyst C, was prepared tocontain 1.5 wt% CoO, 10 wt% Cr₂ O₃, and 15 wt% MoO₃ on a supportcomprising 20 wt% rare earth metal-exchanged Y-type molecular sieves ina matrix of alumina.

A Y-type molecular sieve, designated as "SK-40" and obtained from theLinde Division of Union Carbide Corporation, was exchanged with achloride solution of rare earth metals. A 3,000-gram portion of theSK-40 material was slurried in 8 liters of distilled water. The rareearth chloride solution contained cerium, lanthanum, and praseodymium. A4,000-gram amount of the chloride solution was added to the molecularsieve material and the resulting material was stirred while being heatedto reflux for approximately 1 hour. The solids were then allowed tosettle overnight (approximately 16 hours) and the supernatant layer,about 5,500 milliliters, was syphoned off of the solid material. Then,4,000 grams of the rare earth metal solution and 3,000 milliliters ofdistilled water were added to the solid material and the mixture wasstirred while heating to reflux for 1 hour. The solid material was thenallowed to settle and 6,200 milliliters of supernatant liquid weresyphoned off. Another 4,000 grams of rare earth chloride solution and3,600 milliliters of distilled water were added to the molecular sievesand the resulting composite was stirred while heating to reflux for 1hour. The solid material was then permitted to settle and 6,500milliliters of supernatant liquid were syphoned from the molecularsieves. Subsequently 6,500 milliliters of distilled water were added tothe molecular sieve material and resulting composite was stirred withheating for 1 hour at a temperature of 210° F. (99° C.). The slurry wasfiltered and dried at 250° F. (121° C.) for at least 1 hour and thencalcined in air at a temperature of 1,340° F. (727° C.).

The above 3-step exchange with the rare earth metal solution wasrepeated with the exception that 2,000 grams of the chloride solutionwere employed and 400 grams of ammonium nitrate were added during thelast exchange step. The exchanged material was then washed 4 times withdistilled water as above and filtered. The filter cake was driedovernight (approximately 16 hours) at a temperature of 250° F. (121°C.).

The resulting molecular sieve was found to be 100% crystalline and tocontain the following elements: 13.3 wt% aluminum, 27.9 wt% silicon, 7.2wt% cerium, 3.8 wt% lanthanum, 2.7 wt% sodium, and approximately 1 wt%praseodymium.

A 90-gram portion of the rare earth metal-exchanged molecular sieve wasground and screened to pass through a 100-mesh screen (Tyler), made upinto a paste by the addition of distilled water, and added to 3,600grams of a PHF-alumina sol (approximately 10 wt% solids) obtained fromthe American Cyanamid Company. The resulting mixture was blended in alarge blender for 15 minutes. Then 250 cubic centimeters of a solutionthat had been prepared by mixing equal amounts of distilled water andconcentrated ammonium hydroxide were added to the blend to gel the sol.Two of these batches were made and combined and dried at a temperatureof 250° F. (121° C.) for approximately 64 hours (over the weekend) incirculating air. The dried material was subsequently ground and sievedto a 100-mesh material, mulled with distilled water, and extruded as5/64-inch extrudates. The extrudates were dried for 2 hours at atemperature of 250° F. (121° C.) and then calcined in air at atemperature of 1,000° F. (538° C.) for 2 hours.

A 147-gram portion of the calcined rare earth metal-exchanged molecularsieve in a matrix of alumina material was added to a solution that hadbeen prepared by adding 33.2 grams of (NH₄)₂ Cr₂ O₇ in 140 millilitersof distilled water. This mixture was then allowed to stand for 1 hourand then dried under a heat lamp. The dried chromium-containing materialwas then impregnated with a solution that had been prepared bydissolving 36.8 grams of ammonium molybdate in distilled water andadding to the solution 11.65 grams of Co(NO₃)₂.6H₂ O. The mixture wasallowed to stand for approximately 1 hour and subsequently dried under aheat lamp. The dried impregnated material was then calcined for 1 hourin air at a temperature of 1,000° F. (538° C.).

A 20-cubic centimeter sample of Catalyst C, as 14/20-mesh particles, wascharged to the reactor of a bench-scale pilot plant and was tested forits ability to hydrodenitrogenate and hydrocrack Feed No. 1. The resultsof this test, Test No. 3, are presented hereinbelow in Table IV.

                                      TABLE IV                                    __________________________________________________________________________    DATA FOR TEST NO. 3, CATALYST C                                               Hours on Stream                                                                           19  43  67  91  115 139 163 187                                   __________________________________________________________________________    Temp., °F.                                                                         782 778 --  --  778 778 779 779                                   °C.  417 415 --  --  415 415 415 415                                   Pressure, psig                                                                            1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                 kPa         12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                LHSV, hr.sup.-1                                                                           0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5                                   Gravity, °API                                                                      52.4                                                                              50.8                                                                              45.4                                                                              41.7                                                                              39.8                                                                              39.1                                                                              38.6                                                                              39.1                                  Carbon, wt %                                                                              --  --  --  --  --  86.2                                                                              --  --                                    Hydrogen, wt %                                                                            --  --  --  --  --  13.8                                                                              --  --                                    Nitrogen, ppm                                                                             17  2   2   3   9   31  23  27                                    Sulfur, ppm 347 328 57  160 280 151 250 160                                   Pour Point, °F.                                                                    --  --  --  --  --  75  --  --                                    °C.  --  --  --  --  --  24  --  --                                    Viscosity, cst                                                                            --  --  --  --  --  3.48                                                                              --  --                                    (40° C.)                                                               IBP, °C.                                                                           --  --  --  --  --  40  --  --                                    IBP - 182° C., wt %                                                                --  --  --  --  --  13.6                                                                              --  --                                    182° C.-343° C.,                                                            --  --  --  --  --  57.4                                                                              --  --                                    wt %                                                                          343° C..sup.+, wt %                                                                --  --  --  --  --  29.0                                                                              --  --                                    FBP, °C.                                                                           --  --  --  --  --  516 --  --                                    JP-4 Fraction,                                                                            --  --  --  --  --  34.7                                                                              --  --                                    wt %                                                                          Gas rate, SCFB                                                                            --  --  --  --  --  11.1                                                                              --  --                                    × 10.sup.3                                                              Hydrogen consumption,                                                                     --  --  --  --  --  1,470                                                                             --  --                                    SCFB                                                                          Wt % recovered                                                                            --  --  --  --  --  100 --  --                                    Wt % C.sub.1 -C.sub.4 on                                                                  --  --  --  --  --  2.8 --  --                                    Feed                                                                          __________________________________________________________________________

The results presented in Table IV indicate that Catalyst C, whencompared to Catalyst A, did a very good job in reducing the amount ofnitrogen in the shale oil but only accomplished a small amount ofhydrocracking as indicated by the pour point of 75° F. (23.9° C.).

EXAMPLE IV

A fourth catalyst, hereinafter identified as Catalyst D, was prepared.This catalyst contained a support comprising a ZSM-5 aluminosilicatesuspended and distributed throughout a matrix of alumina. The ZSM-5aluminosilicate was prepared first. A 37.2-gram portion of sodiumhydroxide was dissolved in 400 milliliters of distilled water. A207.9-gram portion of tetra-n-propylammonium bromide was added to thesolution and dissolved therein. Then 42 grams of sodium aluminate wereadded to the solution and dissolved therein. Subsequently, 1,077 gramsof Ludox AS-30 (30% SiO₂) were added to the solution and sufficientdistilled water was added to the resulting blend to make a total volumeof 1,800 milliliters. The resulting material was then placed in a tefloncontainer and into an autoclave. The material was then maintained at atemperature between 450° F. (232° C.) to 470° F. (243° C.) for 6 days.The crystalline material was removed from the autoclave and washed withhot distilled water by reslurrying three times. The crystalline materialwas dried in air at 250° F. (121° C.) overnight (approximately 16 hours)and calcined in air for 3 hours at a temperature of 1,000° F. (538° C.).The resulting material was examined by X-ray diffraction and found to beZSM-5 aluminosilicate material.

A 389-gram portion of the ZSM-5 molecular sieve was exchanged threetimes by slurrying in 3,000 milliliters of distilled water containing202 grams of ammonium nitrate, filtering after each exchange, washingthree times by reslurrying in 3,500 milliliters of distilled water, andfiltering after each wash. The washed and exchanged ZSM-5 material wasthen dried in air overnight (approximately 16 hours) at a temperature of250° F. (121° C.) and calcined in air for 3 hours at a temperature of1,000° F. (538° C.).

This hydrogen form of ZSM-5 material was found to contain 370 parts permillion of sodium, 84.9 wt% of silica, and 3.7 wt% alumina. X-raydiffraction analysis showed it to be 84% crystalline and to have theX-ray diffraction pattern of ZSM-5 material.

A 90-gram portion of the hydrogen-form ZSM-5 molecular sieves was groundand screened to pass through 100-mesh screen (Tyler). It was made into asemi-paste material by the addition of distilled water. It was thenadded in portions to 3,600 grams of PHF-alumina sol (approximately 10wt% solids) obtained from the American Cyanamid Company. The mixture wasblended in a large blender after the addition of each portion of theZSM-5 material. After all of the molecular sieve had been added to thesol, stirring of the blend continued for a time within the range ofabout 10 to 15 minutes. Then 250 cubic centimeters of a solution havingbeen prepared with equal amounts of concentrated ammonium hydroxide anddistilled water were added to the slurry and the mixture was immediatelyblended until the sol gelled. This procedure was repeated. Both batchesof the final gel were combined and dried in air overnight at atemperature of 250° F. (121° C.) in circulating air.

The dried material was ground and screened to a 100-mesh material(Tyler). The resulting ground material was mulled with distilled waterand extruded to form 5/64-inch extrudates, which were then dried instatic air overnight (approximately 16 hours) at a temperature of 250°F. (121° C.). The dried extrudates were calcined in air for at least 4hours at a temperature of 1,000° F. (538° C.). This material wasprepared to contain 20 wt% ZSM-5 molecular sieves suspended in anddispersed throughout a matrix of alumina.

A 147-gram portion of the calcined extrudates was impregnated with asolution that had been prepared by dissolving 33.2 grams of (NH₄)₂ Cr₂O₇ in 145 milliliters of distilled water. The resulting composite wasallowed to stand over the weekend (approximately 64 hours). Then it wascalcined for 11/2 hours at a temperature of 1,000° F. (538° C.) and thematerial was then impregnated with a solution that had been prepared bydissolving 11.65 grams of Co(NO₃)₂.6H₂ O and 36.8 grams of (NH₄)₆ Mo₇O₂₄.4H₂ O in 125 milliliters of distilled water. This solution was addedto the solid material with stirring. After standing for 1 hour, theresulting material was dried under a heat lamp for 2 hours and then inan oven in air for 2 hours at a temperature of 250° F. (121° C.). Thedried material was calcined for 2 hours in air at a temperature of1,000° F. (538° C.). The resultant material, Catalyst D, was prepared tocontain 1.5 wt% CoO, 10 wt% Cr₂ O₃, and 15 wt% MoO₃ on a supportcontaining 20 wt% ZSM-5 molecular sieves suspended in and distributedthroughout a matrix of alumina, the amount of ZSM-5 molecular sievebeing based upon the weight of the support and the amounts of the oxidesof the hydrogenation metals being based upon the weight of the totalcatalyst.

The sample of the catalyst, as 14/20-mesh particles, was charged to thereactor of the small-scale test unit and was tested for its ability tohydrodenitrogenate and hydrocrack Feed No. 1. The results of this test,Test No. 4, are presented hereinbelow in Table V.

                                      TABLE V                                     __________________________________________________________________________    DATA FOR TEST NO. 4, CATALYST D                                               Hours on Stream                                                                           23  47  71  95  119 143 167 191 215 239                           __________________________________________________________________________    Temp , °F.                                                                         781 781 781 781 --  --  781 781 781 781                           °C.  417 417 417 417 --  --  417 417 417 417                           Pressure, psig                                                                            1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                         kPa         12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                        LHSV, hr.sup.-1                                                                           0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5                           Gravity, °API                                                                      40.5                                                                              39.7                                                                              40.2                                                                              39.6                                                                              39.9                                                                              40.7                                                                              40.7                                                                              40.8                                                                              39.7                                                                              39.7                          Carbon, wt %                                                                              --  --  86.20                                                                             --  --  --  --  86.13                                                                             --  --                            Hydrogen, wt %                                                                            --  --  13.79                                                                             --  --  --  --  13.75                                                                             --  --                            Nitrogen, ppm                                                                             23  44  45  42  32  31  29  34  34  32                            Sulfur, ppm 165 139 61  102 120 374 360 91  120 190                           Pour Point, °F.                                                                    --  --  -15 --  --  --  --  -10 --  --                            °C.  --  --  -26 --  --  --  --  -23 --  --                            Viscosity, cst                                                                            --  --  2.64                                                                              --  --  --  --  2.72                                                                              --  --                            (40° C.)                                                               IBP, °C.                                                                           --  --  33  --  --  --  --  -17 --  --                            IBP - 182° C., wt %                                                                --  --  21.8                                                                              --  --  --  --  20.8                                                                              --  --                            182° C.-343° C.,                                                            --  --  60.7                                                                              --  --  --  --  59.6                                                                              --  --                            wt %                                                                          343° C..sup.+, wt %                                                                --  --  17.5                                                                              --  --  --  --  18.6                                                                              --  --                            FBP, °C.                                                                           --  --  509 --  --  --  --  520 --  --                            JP-4 Fraction,                                                                            --  --  48.0                                                                              --  --  --  --  46.2                                                                              --  --                            wt %                                                                          Gas rate, SCFB                                                                            --  --  17.2                                                                              --  --  --  --  11.5                                                                              --  --                            × 10.sup.3                                                              Hydrogen consumption,                                                                     --  --  1,540                                                                             --  --  --  --  1,505                                                                             --  --                            SCFB                                                                          Wt % recovered                                                                            --  --  100.5                                                                             --  --  --  --  100.7                                                                             --  --                            Wt % C.sub.1 -C.sub. 4 on                                                                 --  --  3.9 --  --  --  --  3.7 --  --                            Feed                                                                          __________________________________________________________________________

The results of Test No. 4 demonstrate that Catalyst D providedsatisfactory hydrodenitrogenation and hydrocracking when compared withthe performance of Catalyst A.

EXAMPLE V

A fifth catalyst, hereinafter identified as Catalyst E, was prepared andtested for its ability to hydrodenitrogenate and hydrocrack Feed No. 1.

A crystalline borosilicate prepared by ArChem Company was determined byX-ray diffraction analysis to be crystalline AMS-1B borosilicate.

A 90-gram portion of the hydrogen form of AMS-1B was suspended insufficient distilled water (approximately 150 milliliters) to obtain amixture having a sauce-like consistency. This mixture was then added to3,600 grams of PHF-alumina sol (10 wt% solids), obtained from theAmerican Cyanamid Company. The resulting composite was then thoroughlymixed and 400 milliliters of a solution that was prepared by mixingequal amounts of concentrated ammonium hydroxide and distilled waterwere added and mixed to provide a gel. The resulting gel was removedfrom the mixer and placed in a large pan and dried in an oven at atemperature of 250° F. (121° C.) for at least an hour. A second batchwas prepared exactly as the first batch described hereinabove. Afterboth batches were dried, they were mixed together and ground to passthrough a 100-mesh screen (Tyler). This 100-mesh material was mulledwith distilled water and extruded to form 5/64-inch extrudates and theextrudates were dried at 250° F. (121° C.) for at least an hour andsubsequently in air overnight (approximately 16 hours) at a temperatureof 1,000° F. (538° C.). During the mulling procedure for the formationof the extrudates, the fine powder became too wet and some additionalPHF-alumina was added to the material to dry it.

A 294-gram portion of the calcined extrudates was impregnated with asolution that had been prepared by dissolving 66.4 grams of (NH₄)₂ Cr₂O₇ in 270 milliliters of distilled water. The excess liquid was decantedand the impregnated material was calcined overnight (approximately 16hours) in air at a temperature of 1,000° F. (538° C.). The followingmorning, the excess liquid was added to the catalyst and the materialwas calcined again. The calcined material was then impregnated with asolution that had been prepared by dissolving 73.6 grams of (NH₄)₆ Mo₇O₂₄.4H₂ O in 200 milliliters of distilled water. The impregnatedmaterial was calcined at 1,000° F. (538° C.) over the weekend(approximately 64 hours).

A 190-gram portion of the molybdenum-containing catalyst was impregnatedwith a solution that had been prepared by dissolving 11.65 grams ofCo(NO₃)₂.6H₂ O in 100 milliliters of distilled water. The resultingmaterial was calcined at a temperature of 1,000° F. (538° C.) for atleast 1 hour and then ground and screened to a 14/20-mesh material,i.e., a material that would pass through a 14-mesh screen (Tyler) but beretained upon a 20-mesh screen (Tyler).

The resultant catalyst, Catalyst E, was prepared to contain 1.5 wt% CoO,10 wt% Cr₂ O₃, and 15 wt% MoO₃ on a support comprising 20 wt%hydrogen-form AMS-1B crystalline borosilicate.

A 20-cubic centimeter portion of Catalyst E was loaded into a reactor ofa small-scale test unit and was tested for its ability tohydrodenitrogenate and hydrocrack Feed No. 1. The results of this test,Test No. 5, are presented hereinbelow in Table VI.

                                      TABLE VI                                    __________________________________________________________________________    DATA FOR TEST NO. 5, CATALYST E                                               Hours on Stream                                                                           20  44  68  92  116 140 164 188 212 236 260                       __________________________________________________________________________    Temp., °F.                                                                         --  --  780 780 780 780 780 --  --  781 782                       °C.  --  --  416 416 416 416 416 --  --  417 417                       Pressure, psig                                                                            1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                     kPa         12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                    LHSV, hr.sup.-1                                                                           0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5                       Gravity, °API                                                                      42.5                                                                              42.0                                                                              41.8                                                                              42.7                                                                              41.0                                                                              41.2                                                                              42.2                                                                              39.4                                                                              38.3                                                                              39.4                                                                              41.0                      Carbon, wt %                                                                              --  --  --  86.12                                                                             --  --  --  --  --  --  86.3                      Hydrogen, wt %                                                                            --  --  --  13.87                                                                             --  --  --  --  --  --  13.7                      Nitrogen, ppm                                                                             16  5   5   5   4   4   3   359 425 81  27                        Sulfur, ppm 205 121 23  47  14  10  --  208 301 264 90                        Pour Point, °F.                                                                    --  --  --  -60 --  --  --  --  --  --  -30                       °C.  --  --  --  -51 --  --  --  --  --  --  -34                       Viscosity, cst                                                                            --  --  --  2.22                                                                              --  --  --  --  --  --  2.34                      (40° C.)                                                               IBP, °C.                                                                           --  --  --  -4  --  --  --  --  --  --  -26                       IBP - 182° C., wt %                                                                --  --  --  22.0                                                                              --  --  --  --  --  --  19.4                      182° C.-343° C.,                                                            --  --  --  59.7                                                                              --  --  --  --  --  --  60.1                      wt %                                                                          343° C..sup.+, wt %                                                                --  --  --  18.3                                                                              --  --  --  --  --  --  20.5                      FBP, °C.                                                                           --  --  --  486 --  --  --  --  --  --  490                       JP-4 Fraction,                                                                            --  --  --  48.0                                                                              --  --  --  --  --  --  44.4                      wt %                                                                          Gas rate, SCFB                                                                            --  --  --  12.9                                                                              --  --  --  --  --  --  15.1                      × 10.sup.3                                                              Hydrogen consumption,                                                                     --  --  --  1,610                                                                             --  --  --  --  --  --  1,510                     SCFB                                                                          Wt % recovered                                                                            --  --  --  102.3                                                                             --  --  --  --  --  --  101                       Wt % C.sub.1 -C.sub.4 on                                                                  --  --  --  4.7 --  --  --  --  --  --  4.7                       Feed                                                                          __________________________________________________________________________

The results of Test No. 5, show that Catalyst E is a very good catalystfor the hydrodenitrogenation and hydrocracking of the whole shale oil.

EXAMPLE VI

A sixth catalyst, Catalyst F, was prepared and tested for its ability tohydrodenitrogenate and hydrocrack Feed No. 1.

A 90-gram portion of Zeolon-H synthetic mordenite molecular sieves,obtained from the Norton Chemical Company, was ground and screened topass through a 100-mesh screen (Tyler). This 100-mesh material was thenmade into a slurry by adding distilled water and the resulting slurrywas added at one time to 3,600 grams of PHF-alumina sol (10 wt% solids),obtained from the American Cyanamid Company, in a large blender. Theresulting mixture was blended for 15 minutes. Then 250 cubic centimetersof a solution prepared by mixing equal amounts of distilled water andconcentrated ammonium hydroxide were added thereto. The resultingmaterial was blended immediately until solid appeared. The aboveprocedure was repeated and the material obtained therefrom was combinedwith that obtained from the first batch. The combined product was driedat a temperature of 250° F. (121° C.) in circulating air over theweekend (approximately 64 hours).

The resulting dried material was ground and screened to pass through100-mesh screen (Tyler) and then mulled with distilled water and formedinto 5/64-inch extrudates which were dried in air for 2 hours at atemperature of 250° F. (121° C.). The dried extrudates were calcined forat least 4 hours at a temperature of 1,000° F. (538° C.).

The calcined material was impregnated with a solution that had beenprepared by dissolving 33.2 grams of (NH₄)₂ Cr₂ O₇ in 140 cubiccentimeters of distilled water. A 147-gram portion of the calcinedextrudates was used. The resulting composite was allowed to stand forapproximately 1 hour and dried under a heat lamp. The dried material wasimpregnated with a solution that had been prepared by dissolving 36.8grams of ammonium molybdate in distilled water and then 11.65 grams ofcobalt nitrate in the solution, sufficient water being used to result ina final volume of 120 cubic centimeters. The solution was added to thecatalytic material and the mixture was allowed to stand for 1 hour. Thematerial was dried under a heat lamp and calcined for at least 1 hour inair at a temperature of 1,000° F. (538° C.). This catalyst, Catalyst F,was prepared to contain 1.5 wt% CoO, 10 wt% Cr₂ O₃, and 15 wt% MoO₃ on asupport comprising 20 wt% hydrogen-form Zeolon and alumina.

A 20-cubic centimeter portion of Catalyst F was loaded into a testreactor and tested in a small-scale test unit for its ability tohydrodenitrogenate and hydrocrack Feed No. 1. The results of this test,Test No. 6, are presented hereinbelow in Table VII.

                                      TABLE VII                                   __________________________________________________________________________    DATA FOR TEST NO. 6, CATALYST F                                               Hours on Stream                                                                           20  44  68  92  116 140 164                                       __________________________________________________________________________    Temp., °F.                                                                         780 --  --  780 780 779 780                                       °C.  416 --  --  416 416 415 416                                       Pressure, psig                                                                            1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                     kPa         12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                    LHSV, hr.sup.-1                                                                           0.5 0.5 0.5 0.5 0.5 0.5 0.5                                       Gravity, °API                                                                      38.8                                                                              38.3                                                                              38.2                                                                              38.0                                                                              39.0                                                                              38.4                                                                              38.2                                      Carbon, wt %                                                                              --  --  --  --  86.2                                                                              --  --                                        Hydrogen, wt %                                                                            --  --  --  --  13.7                                                                              --  --                                        Nitrogen, ppm                                                                             85  80  84  86  57  60  72                                        Sulfur, ppm 306 230 122 84  70  140 141                                       Pour Point, °F.                                                                    --  --  --  --  65  --  --                                        °C.  --  --  --  --  18  --  --                                        Viscosity, cst                                                                            --  --  --  --  3.27                                                                              --  --                                        (40° C.)                                                               IBP, °C.                                                                           --  --  --  --  11  --  --                                        IBP - 182° C., wt %                                                                --  --  --  --  14.3                                                                              --  --                                        182° C.-343° C.,                                                            --  --  --  --  57.7                                                                              --  --                                        wt %                                                                          343° C..sup.+, wt %                                                                --  --  --  --  28.0                                                                              --  --                                        FBP, °C.                                                                           --  --  --  --  501 --  --                                        JP-4 Fraction,                                                                            --  --  --  --  35.3                                                                              --  --                                        wt %                                                                          Gas rate, SCFB                                                                            --  --  --  --  8.0 --  --                                        × 10.sup.3                                                              Hydrogen consumption,                                                                     --  --  --  --  1,450                                                                             --  --                                        SCFB                                                                          Wt % recovered                                                                            --  --  --  --  98.6                                                                              --  --                                        Wt % C.sub.1 -C.sub.4 on                                                                  --  --  --  --  3.1 --  --                                        Feed                                                                          __________________________________________________________________________

The results shown in Table VII indicate that Catalyst F does not provideas much hydrodenitrogenation as the other catalysts discussedhereinabove. In addition, it does provide as much hydrocracking of theshale oil as does Catalyst C.

EXAMPLE VII

A seventh catalyst, Catalyst G, was prepared and tested for its abilityto hydrodenitrogenate and hydrocrack Feed No. 1.

A 90-gram portion of low-soda Diuturnal-Y-33-200 crystalline molecularsieve, obtained from the Linde Division of Union Carbide Corporation, inthe form of 100-mesh material, that is, a material that would passthrough a 100-mesh screen (Tyler), was made into a paste by the additionof distilled water and blended with 3,600 grams of PHF-alumina sol(approximately 10 wt% alumina) in a large blender. The PHF-alumina solwas obtained from the American Cyanamid Company. The resulting mixturewas blended for about 15 minutes. Then 250 cubic centimeters of asolution prepared by mixing equal amounts of distilled water andconcentrated ammonium hydroxide were added thereto. The resultingmaterial was blended until a solid appeared. The above procedure wasrepeated and the material obtained from the second preparation wascombined with that obtained from the first. The combined product wasdried in an oven in air at a temperature of 250° F. (121° C.) overnight(approximately 16 hours).

The resulting dried material was ground and screened to pass through a100-mesh screen (Tyler) and then mulled with distilled water and formedinto 5/64-inch extrudates, which were dried in air in an oven overnight(approximately 16 hours) at a temperature of 250° F. (121° C.) andcalcined in air at a temperature of 1,000° F. (538° C.) for at least 1hour.

The calcined material was impregnated with a solution that had beenprepared by adding 66.4 grams of (NH₄)₂ Cr₂ O₇ to 200 milliliters ofdistilled water and subsequently adding sufficient water to bring thevolume of the resulting solution to 250 cubic centimeters. A 294-gramportion of the calcined extrudates was used. The resulting composite wasallowed to stand for approximately 1 hour and dried under a heat lamp.The material was then dried in an oven overnight (approximately 16hours) at a temperature of 250° F. (121° C.) and calcined in an oven inair at a temperature of 1,000° F. (538° C.) for at least 1 hour. A166-gram portion of the dried material was impregnated with a solutionthat had been prepared by dissolving 36.8 grams of ammonium molybdate inwater and 11.65 grams of cobalt nitrate in the resulting solution,sufficient water being used to result in a final volume of 110 cubiccentimeters. The solution was added to the catalytic material and themixture was allowed to stand for 1 hour. The material was then driedunder a heat lamp and calcined for at least 1 hour in air at atemperature of 1,000° F. (538° C.). This catalyst, Catalyst G, wasprepared to contain 1.5 wt% CoO, 10 wt% Cr₂ O₃, and 15 wt% MoO₃ on asupport comprising 20 wt% Diuturnal-Y molecular sieves and alumina.

A 20-cubic centimeter portion of Catalyst G was loaded into a testreactor and tested in a small-scale test unit for its ability tohydrodenitrogenate and hydrocrack Feed No. 1. The results of this test,Test No. 7, are presented hereinbelow in Table VIII.

                                      TABLE VIII                                  __________________________________________________________________________    DATA FOR TEST NO. 7, CATALYST G                                               Hours on stream                                                                           19   43  67   91  115  139 163 187 211 235 259 285                __________________________________________________________________________    Temp., °F.                                                                         781  --  --   779 779  779 779 779 --  --  779 779                °C.  416  --  --   415 415  415 415 415 --  --  415 415                Pressure, psig                                                                            1,800                                                                              1,800                                                                             1,800                                                                              1,800                                                                             1,800                                                                              1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800                                                                             1,800              kPa         12,514                                                                             12,514                                                                            12,514                                                                             12,514                                                                            12,514                                                                             12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514                                                                            12,514             LHSV, hr.sup.-1                                                                           0.5  0.5 0.5  0.5 0.5  0.5 0.5 0.5 0.5 0.5 0.5 0.5                Gravity, °API                                                                      45.2 43.9                                                                              41.2 39.4                                                                              39.0 38.7                                                                              38.9                                                                              38.9                                                                              38.6                                                                              38.8                                                                              38.8                                                                              38.8               Carbon, wt %                                                                              --   --  --   --  86.3 --  --  --  --  --  --  86.3               Hydrogen, wt %                                                                            --   --  --   --  13.7 --  --  --  --  --  --  13.7               Nitrogen, ppm                                                                             27   9   7    9   23   37  29  29  27  32  29  48                 Sulfur, ppm 420  720 254  328 115  232 256 367 930 --  40  165                Pour Point, °F.                                                                    --   --  --   --  75   --  --  --  --  --  --  75                 °C.  --   --  --   --  24   --  --  --  --  --  --  24                 Viscosity, cst                                                                            --   --  --   --  3.29 --  --  --  --  --  --  3.58               (40° C.)                                                               IBP, °C.                                                                           --   --  --   --  45   --  --  --  --  --  --  73                 IBP - 182° C., wt %                                                                --   --  --   --  14.5 --  --  --  --  --  --  13.4               182° C.-343° C.,                                                            --   --  --   --  60.6 --  --  --  --  --  --  59.0               wt %                                                                          343° C..sup.+, wt %                                                                --   --  --   --  24.9 --  --  --  --  --  --  27.6               FBP, °C.                                                                           --   --  --   --  506  --  --  --  --  --  --  469                JP-4 Fraction,                                                                            --   --  --   --  37.8 --  --  --  --  --  --  35.7               wt %                                                                          Gas rate, SCFB                                                                            --   --  --   --  12.8 --  --  --  --  --  --  13.4               × 10.sup.3                                                              Hydrogen consumption,                                                                     --   --  --   --  1,380                                                                              --  --  --  --  --  --  1,390              SCFB                                                                          Wt % recovered                                                                            --   --  --   --  99   --  --  --  --  --  --  100                Wt % C.sub.1 -C.sub.4 on                                                                  --   --  --   --  2.5  --  --  --  --  --  --  2.5                Feed                                                                          __________________________________________________________________________

The results shown in Table VIII indicate that Catalyst G providessomewhat better hydrodenitrogenation than Catalyst F and hydrocrackingthat is similar to that provided by Catalysts C and F.

The data that were obtained from those periods of the above-describedtests in which weight balances were made are summarized in Table IXhereinbelow.

                  TABLE IX                                                        ______________________________________                                        SUMMARY OF RESULTS                                                                          PROPERTIES OF PRODUCT                                                                           Pour                                          Test  Period            Nitrogen,                                                                             Point,  JP-4                                  No.   No.     Catalyst  ppm     °C.                                                                            Wt %                                  ______________________________________                                        1     7       A         110     27      38.1                                  2     5       B         15      -1      59.5                                  2     12      B         14       7      52.1                                  3     6       C         31      24      34.4                                  4     3       D         45      -26     48.0                                  4     8       D         34      -23     46.2                                  5     4       E          5      -51     48.0                                  5     11      E         27      -34     44.4                                  6     5       F         57      18      35.3                                  7     5       G         23      24      37.8                                  7     12      G         48      24      35.7                                  ______________________________________                                    

It is interesting to note that each of the molecular sieve-containingcatalysts provided better hydrodenitrogenation of the shale oil thanCatalyst A, the comparative prior-art catalyst which did not contain amolecular sieve zeolite component, and at least comparablehydrocracking. Hence, each, when employed in the process of the presentinvention, provides an operable and an improved process.

Catalysts B, C, D, E, and G provide excellent overall performance whenconverting the above-described shale oil. Each performs in an overallmanner that is superior to that of the standard catalyst, Catalyst A.While any one of the catalysts discussed hereinabove, except Catalyst A,can be used in the process of the present invention, Catalysts B, C, D,E, and G are preferred.

EXAMPLE VIII

An eighth catalyst, Catalyst H, was prepared and tested for its abilityto hydrodenitrogenate and hydrocrack Feed No. 2, a shale oil, theproperties of which are presented hereinafter in Table X.

                  TABLE X                                                         ______________________________________                                        PROPERTIES OF FEEDS NOS. 2 AND 3                                              Feed No.         2               3                                            ______________________________________                                        Carbon, wt %     85.86           85.18                                        Hydrogen, wt %   11.49           11.66                                        Nitrogen, wt %   1.38            0.166                                        Sulfur, wt %     0.73            2.99                                         Oxygen, wt %     0.53            --                                           Bromine No., gm/100 ml                                                                         56              --                                           Gravity, °API                                                                           28.4            18.6                                         Pour Point, °F.                                                                         35              110                                          °C.       1.7             43                                           Viscosity, cst (100° C.)                                                                1.38            11.68                                        650° F. + material, wt %                                                                30.1            98.0                                         Simulated Distillation                                                        (Sim. Dist.), °F. (°C.)                                         IBP              138      (59)   409   (209)                                   5%              228     (109)   671   (355)                                  10%              271     (133)   727   (386)                                  20%              333     (168)   788   (420)                                  30%              388     (198)   829   (443)                                  40%              444     (229)   863   (462)                                  50%              498     (259)   892   (478)                                  60%              567     (297)   918   (492)                                  70%              658     (348)   945   (507)                                  80%              763     (406)   977   (525)                                  90%              864     (462)   1,000 (538)                                  95%              943     (506)   --    --                                     98%              1,018   (548)   --    --                                     Hydrocarbon Type                                                              Analysis (Mass                                                                Spectra), wt %                                                                Paraffins        --              19.7  --                                     Naphthenes       --              34.7  --                                     Monoaromatics    --              12.6  --                                     Polyaromatics &  --              33.0  --                                     Heterocyclics                                                                 ______________________________________                                    

A 90-gram portion of commercially-available rare earth metal-exchangedY-type molecular sieves was ground and screened to pass through a100-mesh screen (Tyler), made up into a paste by the addition ofdistilled water, and added to 3,600 grams of a PHF-alumina sol(approximately 10 wt% solids) obtained from the American CyanamidCompany. The molecular sieves had been obtained from the DavisonChemical Division of W. R. Grace and Co. The resulting mixture wasblended in a large blender for 15 minutes. Then 250 cubic centimeters ofa solution that had been prepared by mixing equal amounts of distilledwater and concentrated ammonium hydroxide were added to the blend to gelthe sol. Two of these batches were made and subsequently combined anddried at a temperature of about 250° F. (121° C.) for approximately 64hours (over the weekend) in circulating air. The dried material was thenground and sieved to a 100-mesh material (Tyler), mulled with distilledwater, and extruded as 5/64-inch (0.2 centimeter) extrudates. Theextrudates were dried for 2 hours at a temperature of about 250° F.(121° C.) and then calcined in air at a temperature of about 1,000° F.(538° C.) for 2 hours. This catalytic support material was prepared tocontain 20 wt% rare earth metal-exchanged Y-type molecular sieves in amatrix of alumina.

A 143-gram portion of the above support material was added to a solutionthat had been prepared by dissolving 33.2 grams of (NH₄)₂ Cr₂ O₇ in 100milliliters of distilled water. This mixture was then permitted to standfor 1 hour, again mixed, and then dried in an oven at a temperature ofabout 250° F. (121° C.) for 2 hours. The dried material was calcined inair overnight (approximately 16 hours) at a temperature of about 1,000°F. (538° C.). The calcined chromium-containing material was subsequentlyimpregnated with a solution that had been prepared by dissolving 27.25grams of Ni(NO₃)₂.6H₂ O and 36.80 grams of (NH₄)₆ Mo₇ O₂₄.4H₂ O in 90milliliters of distilled water. The solution and support material werethoroughly mixed and the mixture was allowed to stand for approximately1 hour, after which the composite was mixed again and placed in an ovenfor 2 hours at a temperature of approximately 250° F. (121° C.). Thedried material was subsequently calcined overnight (approximately 16hours) at a temperature of about 1,000° F. (538° C.).

The finished catalytic material, Catalyst H, was prepared to contain 3.5wt% NiO, 15 wt% MoO₃, and 10 wt% Cr₂ O₃.

A 14.4-cubic centimeter sample of Catalyst H, as 14/20-mesh particles(U.S. Sieve Series), was charged to the reactor of a bench-scale testunit as described hereinabove and was tested for its ability tohydrodenitrogenate and hydrocrack the shale oil identified as Feed No.2. The results of this test, Test No. 8, are presented hereinbelow inTable XI.

                  TABLE XI                                                        ______________________________________                                        DATA FOR TEST NO. 8, CATALYST H, FEED NO. 2                                   Hours on Stream                                                                           108     180             300                                       ______________________________________                                        Temperature, °F.                                                                   760     760               780                                     °C.  404     404               416                                     Pressure, psig                                                                            1,800   1,800             1,800                                   kPa         12,514  12,514            12,514                                  Hydrogen, SCFB                                                                            10,040  10,590            10,520                                  LHSV, hr.sup.-1                                                                           0.5     0.5               0.5                                     Product Properties                                                            Gravity, °API                                                                      40.4    40.3              43.5                                    Pour Point, °F.                                                                            50                25                                      °C.          10                -3.9                                    Viscosity, cst      2.12              1.62                                    (40° C.)                                                               Carbon, wt %        86.45             86.28                                   Hydrogen, wt %      13.53             13.72                                   Sulfur, ppm         19                9                                       Nitrogen, ppm                                                                             174     206               2                                       Sim. Dist., °F. (°C.)                                           IBP                 178      (81)     163    (73)                              5%         244     (118)        237  (114)                                   20%                 328     (165)     308   (153)                             50%                 454     (236)     424   (218)                             80%                 630     (332)     570   (299)                             95%                 803     (439)     743   (395)                             Product Yield,                                                                wt %                                                                          C.sub.1 -C.sub.4    2.4               5.5                                     IBP - 182° C.                                                                              27.0              32.1                                    182°-343° C.                                                                        53.2              51.9                                    343° C..sup.+                                                                      17.4                 10.5                                         ______________________________________                                    

The results shown in Table XI indicate that Catalyst H does provide verygood hydrodesulfurization, hydrodenitrogenation, and hydrocracking ofFeed No. 2, a shale oil. Hydrocracking is measured by the conversion ofthe 650° F.⁺ feed to 650° F.⁻ products.

EXAMPLE IX

Catalyst H was also tested for its ability to convert a heavy vacuum gasoil, Feed No. 3. The properties of Feed No. 3 are presented hereinabovein Table X.

A 16-cubic centimeter portion of Catalyst H was loaded into a testreactor and tested with Feed No. 3 in a bench-scale test unit asdescribed hereinabove. The results of this test, Test No. 9, arepresented hereinbelow in Table XII.

                                      TABLE XII                                   __________________________________________________________________________    DATA FOR TEST NO. 9, CATALYST H, FEED NO. 3                                   Hours on Stream                                                                          88     112 160    256     424    496                               __________________________________________________________________________    Temperature, °F.                                                                  740    780 780    780     770    740                               °C. 393    416 416    416     410    393                               Pressure, psig                                                                           1,800  1,800                                                                             1,800  1,800   1,800  1,800                             kPa        12,514 12,514                                                                            12,514 12,514  12,514 12,514                            Hydrogen, SCFB                                                                           11,950 13,780                                                                            9,460  19,340  20,200 9,920                             LHSV, hr.sup.-1                                                                          1.25   1.25                                                                              1.25   0.625   0.625  1.25                              Product Properties                                                            Gravity, °API                                                                     27.7       31.1   51.2    33.2   26.0                              Pour Point, °F.                                                                   90         95     -70     85     105                               °C. 32.2       35     -56.7   29.4   41                                Viscosity, cst                                                                           5.68       2.85   0.82    1.90   5.81                              (100° C.)                                                              Carbon, wt %                                                                             86.97      87.18  86.09   87.06  87.11                             Hydrogen, wt %                                                                           12.90      12.78  13.89   12.93  12.68                             Sulfur, ppm       125 190    254     52     1,270                             Nitrogen, ppm                                                                            535        123    2       22     799                               Sim. Dist., °F. (°C.)                                           IBP        295 (146)  117  (47)                                                                            -29 (-34)                                                                             117  (47)                                                                            104 (40)                           5%        510 (266)  284 (140)                                                                            115 (46)                                                                              242 (117)                                                                            270 (132)                         20%        688 (365)  525 (274)                                                                            199 (93)                                                                              438 (226)                                                                            582 (305)                         50%        817 (436)  747 (397)                                                                            295 (146)                                                                             653 (345)                                                                            798 (426)                         80%        917 (492)  886 (475)                                                                            415 (213)                                                                             842 (450)                                                                            930 (499)                         95%        994 (534)  971 (522)                                                                            536 (280)                                                                             845 (452)                                                                            --  --                            Product Yield, wt %                                                           C.sub.1 -C.sub.4                                                                         0.6        1.6    9.7     2.9    0.5                               IBP - 182° C.                                                                     1.3        8.2    61.2    12.4   8.4                               182°-343° C.                                                               13.3       24.6   28.4    35.7   17.9                              343° C..sup.+                                                                     84.8       65.6   0.7     49.0   73.2                              __________________________________________________________________________

The data presented in Table XII indicate that Catalyst H providessubstantial hydrodesulfurization, hydrodenitrogenation, andhydrocracking of this heavy vacuum gas oil, Feed No. 3.

EXAMPLE X

A ninth catalyst, Catalyst I, was prepared and tested for its ability tohydrodenitrogenate and hydrocrack Feed No. 2, the shale oil.

A 359.71-gram portion of the rare earth metal-exchanged Y-type molecularsieves obtained from Davison Chemical Division of W. R. Grace and Co.was ground and screened to pass through a 100-mesh screen (Tyler) andmixed with 700 milliliters of distilled water. The resulting paste wasadded to 3,558 grams of a PHF-alumina sol (approximately 10 wt% solids)obtained from the American Cyanamid Company. The resulting composite wasblended for 10 minutes. Then a solution prepared by adding 200milliliters of concentrated ammonium hydroxide to 200 milliliters ofdistilled water was rapidly added to the blended material to form a gel.The gel was subsequently dried in air in an oven for 42 hours at atemperature of about 250° F. (121° C.). The dried material was thenground to pass through a 100-mesh screen (Tyler). The ground materialwas mulled with distilled water and extruded as 5/64-inch(0.2-centimeter) extrudates, which were dried overnight (approximately16 hours) in air at a temperature of about 250° F. (121° C.) and thencalcined in air at a temperature of about 1,000° F. (538° C.) for 4hours.

A 143-gram portion of this support material, which was prepared tocontain 50 wt% molecular sieves in a matrix of alumina, was added to asolution that had been prepared by dissolving 33.2 grams of (NH₄)₂ Cr₂O₇ in 130 milliliters of distilled water. After the excess liquid wasremoved under a heat lamp, the impregnated material was dried in an ovenin air for at least 2 hours at a temperature of about 250° F. (121° C.)and then calcined in air for 2 hours at a temperature of about 1,000° F.(538° C.). The calcined chromium-containing material was thenimpregnated with a solution that had been prepared by first dissolving36.8 grams of (NH₄)₆ Mo₇ O₂₄.4H₂ O in 120 milliliters of water to form amolybdenum-containing solution and then dissolving 27.25 grams ofNi(NO₃)₂.6H₂ O in the molybdenum-containing solution. The excess liquidwas removed under a heat lamp, and the material was then dried in air inan oven at a temperature of about 250° F. (121° C.) for at least 2 hoursand calcined in air for 2 hours at a temperature of about 1,000° F.(538° C.). The finished Catalyst I was prepared to contain 3.5 wt% NiO,10 wt% Cr₂ O₃, and 15 wt% MoO₃.

A 14.4-cubic centimeter sample of Catalyst I in the form of 14/20-meshparticles (U.S. Sieve Series), was charged to the reactor of abench-scale test unit as described hereinabove and was tested for itsability to hydrodenitrogenate and hydrocrack Feed No. 2. The results ofthis test, Test No. 10, are presented hereinbelow in Table XIII.

                  TABLE XIII                                                      ______________________________________                                        DATA FOR TEST NO. 10, CATALYST I, FEED NO. 2                                  Hours on Stream                                                                          156            204   276   324                                     ______________________________________                                        Temperature, °F.                                                                  760            780   780   780                                     °C. 404            416   416   416                                     Pressure, psig                                                                           1,800          1,800 1,800 1,800                                   kPa        12,514         12,514                                                                              12,514                                                                              12,514                                  LHSV, hr.sup.-1                                                                          0.5            0.5   0.5   0.5                                     Hydrogen, SCFB                                                                           8,354          11,336                                                                              12,831                                                                              9,000                                   Product                                                                       Properties                                                                    Gravity, °API                                                                     40.4           43.3  47.4  48.0                                    Pour Point, °F.                                                                   50                         -50                                     °C. 10                         -45.6                                   Viscosity, cst                                                                           --                         1.21                                    (40° C.)                                                               Carbon, wt %                                                                             86.34                      86.05                                   Hydrogen, wt %                                                                           13.63                      13.95                                   Sulfur, ppm                                                                              241                        9                                       Nitrogen, ppm                                                                            185            2.3   2.9   1.3                                     Sim. Dist.,                                                                   °F. (°C.)                                                       IBP        179     (82)               160    (71)                              5%        243     (118)              208    (98)                             20%        320     (160)              270   (132)                             50%        449     (232)              356   (180)                             80%        635     (335)              469   (243)                             95%        802     (428)              610   (321)                             Product Yield,                                                                wt %                                                                          C.sub.1 -C.sub.4                                                                         2.5                        6.8                                     IBP - 182° C.                                                                     27.9                       47.5                                    182°-343° C.                                                               42.0                       42.8                                    343° C..sup.+                                                                     27.6                       2.8                                     ______________________________________                                    

The results presented in Table XIII demonstrate that Catalyst I issuitable for hydrodesulfurization, hydrodenitrogenation, andhydrocracking of Feed No. 2, a shale oil.

Catalysts H and I are preferred embodiments of the catalyst of thepresent invention.

They, as well as the other preferred catalysts of the present invention,are not only suitable for the conversion of whole shale oils and anyfraction thereof, but also are suitable for the hydrodenitrogenation andhydrocracking of other distillate hydrocarbon streams containing highconcentrations of nitrogen, such as hydrocarbons derived from coal,hydrocarbons derived from tar sands, and petroleum hydrocarbondistillates.

Another embodiment of the process of the present invention is a processfor the hydrodenitrogenation and hydrocracking of a heavy hydrocarbonstream containing a substantial amount of nitrogen compounds to producemotor fuel components, heater oil components, and a feedstock for acatalytic cracking unit. Those hydrocarbon streams containing asubstantial amount of nitrogen compounds that are potential feedstocksfor catalytic cracking units include, but are not limited to, light andheavy vacuum gas oils, coker gas oils, certain fractions of shale oil,tar sands oil, and coal liquids, particularly those boiling in the rangeof about 600° F. (316° C.) to about 1,000° F. (538° C.), and mixturesthereof. Cycle oils and decanted oils can be used as catalytic crackerfeedstocks, but a substantially greater amount of hydrogen is requiredto hydrotreat effectively these latter streams. Moreover, thehydrotreating is carried out to reduce the nitrogen level to a range ofabout 400 ppm (0.04 wt%) to about 1,000 ppm (0.1 wt%). Any furtherreduction is usually unnecessary and may be uneconomical. Suchhydrotreating will reduce also the sulfur content to a value within therange of about 0 ppm (0 wt%) to about 5,000 ppm (0.5 wt%) sulfur,preferably, a value that is less than 3,000 ppm (0.3 wt%). Typicalcracking catalysts can tolerate these nitrogen and sulfur levels.

Accordingly, there is provided a process for the hydrodenitrogenationand hydrocracking of a heavy hydrocarbon stream containing a substantialamount of nitrogen compounds to produce motor fuel components, heateroil components, and a feedstock for a catalytic cracking unit, whichprocess comprises contacting said stream in a reaction zone undersuitable conditions and in the presence of hydrogen with a catalystcomprising a hydrogenation component comprising chromium, molybdenum,and at least one Group VIII metal deposed upon a support comprising acrystalline molecular sieve zeolite selected from the group consistingof an ultrastable, large-pore crystalline aluminosilicate material, aZSM-5-type crystalline aluminosilicate, an AMS-1B crystallineborosilicate, a crystalline Y-type aluminosilicate, and a rare earthmetal-exchanged crystalline Y-type aluminosilicate suspended in anddistributed throughout a matrix of catalytically-active alumina, themetals of said hydrogenation component being present in the elementalform, as oxides, as sulfides, or mixtures thereof, said metal of GroupVIII being present in an amount within the range of about 0.5 wt% toabout 10 wt%, calculated as the oxide of the metal, said molybdenumbeing present in an amount within the range of about 5 wt% to about 25wt%, calculated as MoO₃, and said chromium being present in an amountwithin the range of about 3 wt% to about 15 wt%, calculated as Cr₂ O₃,each amount being based upon the weight of said catalyst, and saidmolecular sieve zeolite being present in an amount within the range ofabout 5 wt% to about 90 wt%, based upon the weight of said support. Thishydrotreating process produces distillate and reduces the nitrogencontent and the sulfur content of the remaining hydrocarbon (gas oil)stream to the above-defined levels that provide superior yields when thestream is catalytically cracked.

As shown hereinabove in Example IX, an embodiment of the process of thepresent invention is a process for the hydrodenitrogenation andhydrocracking of a hydrocarbon stream containing a substantial amount ofnitrogen compounds (a heavy vacuum gas oil) to provide a hydrocarbonstream that contains nitrogen and sulfur levels which a crackingcatalyst can tolerate and, hence, that is suitable as feed to acatalytic cracking unit.

The following examples are being presented to demonstrate further theeffectiveness of the process of the present invention for thehydrotreating of a hydrocarbon stream containing a substantial amount ofnitrogen compounds to provide distillate and a catalytic cracker feed.

EXAMPLE XI

A tenth catalyst, Catalyst J, and an eleventh catalyst, Catalyst K, wereprepared and tested for their abilities to hydrotreat Feed No. 3, theheavy vacuum gas oil.

For each of these catalysts, Aero 100A alumina in the form of 1/32-inch(0.079-centimeter) extrudates, obtained from the American CyanamidCompany, after being calcined in air at a temperature of about 1,000° F.(538° C.), was impregnated with an aqueous solution of (NH₄)₂ Cr₂ O₇.The mixture of alumina support material and solution was allowed tostand for a period of time and then was calcined in air at a temperatureof about 1,000° F. (538° C.) overnight (approximately 16 hours). Thecalcined chromium-containing material was impregnated with an aqueoussolution of either Ni(NO₃)₂.6H₂ O or Co(NO₃)₂.6H₂ O and (NH₄)₆ Mo₇O₂₄.4H₂ O. The mixture of solids and solution was permitted to stand fora short period of time and was calcined subsequently at a temperature ofabout 1,000° F. (538° C.). The finished catalyst was ground to a16/20-mesh material, i.e., a material that will pass through a 16-meshscreen (Tyler), but will be retained upon a 20-mesh screen (Tyler).

Additional information and data relating to the preparation of CatalystsJ and K are presented hereinbelow in Table XIV.

                  TABLE XIV                                                       ______________________________________                                        PREPARATION OF CATALYSTS J AND K                                              Catalyst            J             K                                           ______________________________________                                        Aero 100A Al.sub.2 O.sub.3, gm                                                                    139           147                                         Calcining Time, hr  --            --                                          Calcining Temp., °C.                                                                       538           538                                         First Impregnation                                                            (NH.sub.4).sub.2 Cr.sub.2 O.sub.7, gm                                                             33.2          33.2                                        Distilled H.sub.2 O, ml                                                                           135           145                                         Standing Time, hr   1             6                                           Standing Temp.      room          room                                        Calcining Time, hr  16            16                                          Calcining Temp., °C.                                                                       538           538                                         Second Impregnation                                                           (NH.sub.4).sub.6 Mo.sub.7 O.sub.24.4H.sub.2 O, gm                                                 41.71         41.71                                       Ni(NO.sub.3).sub.2.6H.sub.2 O, gm                                                                 27.20         --                                          Co(NO.sub.3).sub.2.6H.sub.2 O, gm                                                                 --            11.65                                       Distilled H.sub.2 O, ml                                                                           120           120.sup.(1)                                 Standing Time, hr   6             16                                          Standing Temp.      room          room                                        Calcining Time, hr  16            5                                           Calcining Temp., °C.                                                                       538           538                                         Particle Size, mesh (Tyler)                                                                       16/20         16/20                                       Composition, wt %                                                             MoO.sub.3           20.0          14.6                                        Cr.sub.2 O.sub.3    10.5          9.1                                         NiO                 3.5           --                                          CoO                 --            1.5                                         Surface Area, m.sup.2 /gm                                                                         170           --                                          Pore Volume, cc/gm  0.51          --                                          Avg. Pore Diameter, nm                                                                            8.4           --                                          Å               84            --                                          ______________________________________                                         .sup.(1) Sufficient H.sub.2 O used to make 120 ml of solution.           

EXAMPLE XII

Catalysts J and K were tested subsequently with Feed No. 3. WhileCatalysts J and K and the others described and tested in the followingexamples were tested in the same type of equipment and in a manner thatwas similar to that employed in the previous examples, 10 inches of1/8-inch (0.32-centimeter) alundum balls were used as a support for thecatalyst and such alundum balls were used to fill the space in thereactor above the catalyst bed.

Each of these catalysts, including the ones described and tested in thefollowing examples, were subjected to a sulfiding pretreatment. For suchpretreatment, the reactor was first purged with nitrogen for a shortperiod of time after which the temperature of the catalyst bed wasraised to about 300° F. (149° C.) and a gas mixture of 8% hydrogensulfide in hydrogen was passed through the catalyst bed at a pressure ofabout 300 psi (2,069 kPa) and a rate of about 20 liters per hour. Afterabout one hour had elapsed, the temperature was raised to about 400° F.(204° C.). After an additional hour, the flow of the hydrogensulfide-in-hydrogen gas mixture was stopped and a flow of hydrogen at aflow rate of 20 liters per hour was established at a pressure of 1,200psig (8,410 kPa). Hydrocarbon feed was then introduced into the reactorand the temperature of the catalyst bed was raised to the reactiontemperature. This pretreatment procedure was carried out for each of thecatalysts in the following tests with the exception of Catalyst J inTest No. 12. In that case, after the use of the hydrogensulfide-in-hydrogen gas mixture at 400° F. (204° C.), the temperaturewas raised to 700° F. (371° C.) and the gas mixture was employed for anadditional hour at 700° F. (371° C.). Then the flow of the gas mixturewas stopped and replaced with the hydrogen flow, as in the other tests.

The sulfided Catalyst J was tested for its ability to hydrotreat FeedNo. 3 in two tests, Test No. 11 and Test No. 12. The pertinentinformation and data of these two tests are presented hereinbelow inTable XV and Table XVI, respectively.

                                      TABLE XV                                    __________________________________________________________________________    DATA FOR TEST NO. 11, CATALYST J, FEED NO. 3                                  Days on Stream  5       8    12                                               __________________________________________________________________________    LHSV, hr.sup.-1 1.25    1.25 1.25                                             Temp., °F.                                                                             740     780  780                                              °C.      393     416  416                                              Hydrogen Pressure, psi                                                                        1,200   1,200                                                                              1,200                                            kPa             8,343   8,343                                                                              8,343                                            Hydrogen Rate, SCFB                                                                           10,500  19,000                                                                             19,000                                           m.sup.3 /m.sup.3                                                                              1,870   3,384                                                                              3,384                                            Product Properties                                                            Gravity, °API                                                                          27.0    29.6 29.4                                             gm/cc           0.8927       0.8794                                           Pour Point, °F.                                                                        100     --   100                                              °C.      37.8    --   37.8                                             Viscosity at 100° C., cst                                                              5.47    --   3.37                                             Carbon, wt %    87.22   --   87.23                                            Hydrogen, wt %  12.70   --   12.73                                            Sulfur, ppm     390     215  150                                              Nitrogen, ppm   445     160  225                                              Sim. Dist., °F. (°C.)                                           IBP             272  (133)                                                                            --   208  (98)                                         5%             516  (269)                                                                            --   380 (193)                                        20%             686  (364)                                                                            --   587 (308)                                        50%             813  (434)                                                                            --   759 (404)                                        80%             913  (490)                                                                            --   887 (475)                                        95%             983  (529)                                                                            --   983 (529)                                        Hydrodesulfurization (HDS), %                                                                 98.7    99.3 99.5                                             Hydrodenitrogenation (HDN), %                                                                 73.8    91.1 86.8                                             Hydrogen Consumed, SCFB                                                                       625     --   680                                              m.sup.3 /m.sup.3                                                                              111     --   121                                              Product Yield, wt %                                                           C.sub.1 -C.sub.4                                                                              0.6     0.6  1.4                                              IBP - 182° C.                                                                          0.3     1.2  4.1                                              182°-343° C.                                                                    15.6    13.7 28.2                                             343° C..sup.+                                                                          83.5    84.5 66.3                                             __________________________________________________________________________

                                      TABLE XVI                                   __________________________________________________________________________    DATA FOR TEST NO. 12, CATALYST J, FEED NO. 3                                  Days on Stream                                                                              4      7      11     14     18     21                           __________________________________________________________________________    LHSV, hr.sup.-1                                                                             0.625  0.625  0.625  0.625  0.625  0.625                        Temp., °F.                                                                           740    760    780    740    800    740                          °C.    393    404    416    393    427    393                          Pressure, psi 1,200  1,200  1,200  1,200  1,200  1,200                        kPa                                                                           Hydrogen Rate, SCFB                                                                         12,000 12,000 12,000 12,000 12,000 12,000                       m.sup.3 /m.sup.3                                                                            2,137  2,137  2,137  2,137  2,137  2,137                        Product Properties                                                            Gravity, °API                                                                        29.2   31.4   31.1   28.8   32.9   30.0                         g/cc          0.8805 0.8686 0.8702 0.8827 0.8607 0.8762                       Pour Point, °F.                                                                      100    100    100    105    95     105                          °C.    --     --     --     --     --     --                           Viscosity at 100° C., cst                                                            3.72   3.11   2.44   4.21   --     4.58                         Carbon, wt %  87.11  87.09  87.14  87.09  87.22  87.20                        Hydrogen, wt %                                                                              12.89  12.89  12.84  12.87  12.77  12.75                        Sulfur, ppm   17     89     74     64     61     119                          Nitrogen, ppm 89     65     88     241    73     373                          Sim. Dist., °F. (°C.)                                           IBP           336 (169)                                                                            182  (83)                                                                            248 (120)                                                                            267 (131)                                                                            140  (60)                                                                            245 (118)                     5%           486 (252)                                                                            334 (168)                                                                            387 (197)                                                                            417 (214)                                                                            277 (136)                                                                            472 (244)                    20%           647 (342)                                                                            557 (293)                                                                            556 (291)                                                                            660 (349)                                                                            467 (242)                                                                            667 (353)                    50%           790 (421)                                                                            751 (399)                                                                            718 (381)                                                                            805 (429)                                                                            656 (347)                                                                            809 (432)                    80%           905 (485)                                                                            888 (476)                                                                            843 (450)                                                                            915 (491)                                                                            798 (426)                                                                            918 (492)                    95%           993 (534)                                                                            980 (527)                                                                            935 (502)                                                                            998 (537)                                                                            899 (482)                                                                            999 (537)                    HDS, %        99.9   99.7   99.8   99.8   99.8   99.6                         HDN, %        94.6   96.1   94.7   85.5   95.6   77.5                         Hydrogen Consumed, SCFB                                                                     765    830    785    745    800    670                          m.sup.3 /m.sup.3                                                                            136    148    140    133    142    119                          Product Yield, wt %                                                           C.sub.1 -C.sub.4                                                                            0.9    2.2    2.2    0.7    3.4    0.9                          IBP - 182° C.                                                                        0.3    5.9    3.4    1.8    9.9    2.1                          182°-343° C.                                                                  20.2   25.0   31.3   16.5   36.8   15.4                         343° C..sup.+                                                                        78.6   67.0   63.1   81.0   50.0   81.5                         __________________________________________________________________________

The sulfided Catalyst K was tested for its ability to hydrotreat FeedNo. 3 in Test No. 13, the results of which are presented hereinbelow inTable XVII.

                  TABLE XVII                                                      ______________________________________                                        DATA FOR TEST NO. 13, CATALYST K, FEED NO. 3                                  ______________________________________                                        Days on Stream  23       59        79.sup.(1)                                 ______________________________________                                        LHSV, hr.sup.-1 1.2      1.2       1.2                                        Temp., °F.                                                                             740      740       740                                        °C.      393      393       393                                        Hydrogen Pressure,                                                            psi             1,250    1,250     1,250                                      kPa             8,690    8,690     8,690                                      Product Properties                                                            Gravity, °API                                                                          27.1     26.8      27.0                                       gm/cc           0.8922   0.8939    0.8927                                     Sulfur, ppm     480      630       1,570                                      Nitrogen, ppm   634      812       1,050                                      343° C..sup.+  Product, %                                                              83.5     84.0      85.0                                       ______________________________________                                        Days on Stream  99       106       111                                        ______________________________________                                        LHSV, hr.sup.-1 1.2      1.2       1.2                                        Temp., °F.                                                                             740      740       740                                        °C.      393      393       393                                        Hydrogen Pressure,                                                            psi             1,250    1,250     1,250                                      kPa             8,690    8,690     8,690                                      Product Properties                                                            Gravity, °API                                                                          26.8     27.2      27.0                                       gm/cc           0.8939   0.8916    0.8927                                     Sulfur, ppm     660      820       740                                        Nitrogen, ppm   1,180    740       978                                        343° C. Product, %                                                                     85.0     81.5      84.0                                       ______________________________________                                         .sup.(1) Test unit lost hydrogen pressure for several hours about this        time.                                                                    

The results of Tests Nos. 11, 12, and 13 demonstrate the performance ofcatalysts that do not contain crystalline molecular sieve zeolites whenthey are being employed to hydrodenitrogenate, hydrodesulfurize, andpossibly hydrocrack a heavy vacuum gas oil.

EXAMPLE XIII

Six catalysts, each of which contained nickel, chromium, and molybdenumas hydrogenating metals and a support comprising a crystalline molecularsieve zeolite suspended in and distributed throughout a catalyticallyactive alumina, were prepared and tested subsequently for theirabilities to hydrotreat the heavy vacuum gas oil, Feed No. 3. These sixcatalysts are identified hereinafter as Catalysts L, M, N, O, P, and Q.In general, each of these six catalysts was prepared as described in thefollowing paragraphs.

Each catalyst support was prepared. The particular crystalline molecularsieve zeolite material, in a finely-divided form, was made into a pastewith distilled water and added to a sol of an Aero 1000 alumina (about10 wt% solids) obtained from the American Cyanamid Company. Thecomposite of zeolite and alumina sol was thoroughly blended, gelled bymeans of the addition of a 1:1 solution of distilled water andconcentrated ammonium hydroxide, dried in air, ground to pass through a100-mesh screen (Tyler), and extruded to 5/64-inch (0.198-centimeter)extrudates. The extrudates were dried at a temperature of 250° F. (121°C.) for a time within the range of 2 hours to about 16 hours andcalcined in air at a temperature of about 1,000° F. (538° C.) for aperiod of time ranging from at least 1 hour to about 16 hours. In someof the cases, two batches were prepared and combined before theextrudates were made. The calcined extrudates comprised a particularcatalyst support. Information related to the preparation of thesecatalyst supports is presented hereinbelow in Table XVIII.

                                      TABLE XVIII                                 __________________________________________________________________________    CATALYST SUPPORT PREPARATION                                                  Catalyst    L   M    N     O    P   Q                                         __________________________________________________________________________    Zeolite Material,                                                                         USAM                                                                              HZSM-5                                                                             HAMS-1B                                                                             HEZ-55                                                                             DY  REY                                       gm/batch    681 90   90    --   90  90                                        Alumina Sol,                                                                              15,890                                                                            3,600                                                                              3,600 --   3,600                                                                             3,600                                     gm/batch                                                                      No. of Batches                                                                            1   2    2     --   2   2                                         Particle Size of Zeolite,                                                                 --  100  --    --   100 100                                       mesh (Tyler)                                                                  1:1 NH.sub.4 OH sol'n., cc                                                                800 250  400   --   250 250                                       Drying of gel.                                                                Time, hr    16  16   --    --   --  ≈60                               Temp., °C.                                                                         121 121  121   --   121 121                                       Particle Size Before Ex-                                                                  100 100  100   --   100 100                                       trusion, mesh (Tyler)                                                         Drying of Extrudate                                                           Time, hr    16  16   -.sup.(1)                                                                           16   16  2                                         Temp., °C.                                                                         121 121  121   121  121 121                                       Calcining of Extrudate                                                        Time, hr    3   >4   16    ≈2                                                                         >1  2                                         Temp., °C.                                                                         538 538  538   538  538 538                                       Extrudate size, cm                                                                        0.198                                                                             0.198                                                                              0.198 0.198                                                                              0.198                                                                             0.198                                     Molecular Sieve in                                                                        30  20   20    20   20  20                                        Support, %                                                                    __________________________________________________________________________     .sup.(1) During mulling for extrusion, Al.sub.2 O.sub.3 added to aid          drying.                                                                  

The ultrastable, large-pore crystalline aluminosilicate material wasobtained as Z-14US molecular sieves from the Davison Chemical Divisionof W. R. Grace & Co. The Z-14US material, which contained 2.49 wt%sodium, was exchanged with ammonium nitrate solution and washed withdistilled water in order to reduce its sodium content. After the cationexchange, the sodium level was 0.13 wt% sodium. This exchanged USmolecular sieve is identified herein as USAM.

Prior to its use in a catalyst support, ZSM-5-type molecular sievematerial was slurried in distilled water and cation exchanged withammonium nitrate solution. A 389-gram portion of the ZSM-5 material wasslurried in 3,000 milliliters of distilled water and exchanged threetimes with 202 grams of (NH₄)(NO₃). The material was filtered after eachexchange step. The exchanged material was then washed three times byreslurrying in 3,500 milliliters of distilled water and filtered aftereach wash. The washed, exchanged material was dried overnight(approximately 16 hours) in air at a temperature of 250° F. (121° C.)and calcined in air for three hours at a temperature of 1,000° F. (538°C.). The calcined material was the hydrogen form of the ZSM-5-typemolecular sieve material and is identified herein as HZSM-5. X-raydiffraction analysis indicated that the HZSM-5 material was 84%crystalline material and provided the ZSM-5 X-ray diffraction pattern.

Crystalline AMS-IB borosilicate material was exchanged with ammoniumnitrate solution, dried, and calcined to provide the hydrogen form ofthe material, which is identified herein as HAMS-IB.

The fluid cracking catalyst HEZ-55, which contained a faujasiticzeolitic molecular sieve component, was obtained from the HoudryCorporation. It is identified herein as HEZ-55.

A catalyst support was made with Diuturnal-Y molecular sieves obtainedfrom the Linde Division of Union Carbide Corporation. These sieves areidentified hereinafter as DY molecular sieves.

A rare earth metal-exchanged Y-type zeolite was obtained by exchanging3,000 grams of SK-40 molecular sieves obtained from the Linde Divisionof Union Carbide Corporation. The SK-40 material was slurried in eightliters of distilled water and the slurry was added to 4,000 grams ofrare earth chloride solution (approximately 60% crystals) obtained fromthe Ventron Division of Alfa Inorganics. The resulting mixture wasstirred as it was heated to reflux for a period of about one hour andthe solids were allowed to settle thereafter overnight. Subsequently thesupernatant liquid (5,500 milliliters) was siphoned off. The solidmaterial was exchanged four times with 4,000 grams of rare earthchloride solution and 3,000 milliliters of water each time. Thesupernatant liquid (6,200 milliliters) was siphoned off. Then it wasexchanged four times with 4,000 grams of rare earth chloride solutionand 3,600 milliliters of water each time and the supernatant liquid(6,500 milliliters) was siphoned off. The material was then filtered,dried at a temperature of about 250° F. (121° C.) for a period of 16hours, and calcined in air for three hours at a temperature of about1,430° F. (777° C.). The calcined material was again exchanged with rareearth chloride solution three times, using about 2,000 grams of rareearth chloride solution each time and adding 400 grams of ammoniumnitrate, (NH₄)(NO₃), during the last exchange. The exchanged materialwas then washed with distilled water four times, filtered, andfilter-cake dried at a temperature of 250° F. (121° C.) overnight(approximately 16 hours). This exchanged, rare earth metal Y zeolite isidentified herein as REY.

Each support was impregnated with solutions of metal salts in order toprovide a final catalytic composition containing nickel, chromium, andmolybdenum as hydrogenating metals. The chromium was added first bymeans of an aqueous solution of (NH₄)₂ Cr₂ O₇. After thechromium-impregnated material was dried and calcined, it was impregnatedeither by means of a single solution containing both Ni(NO₃)₂.6H₂ O and(NH₄)₆ Mo₇ O₂₄.4H₂ O or by a solution of (NH₄)₆ Mo₇ O₂₄.4H₂ O followedafter drying and calcination by a solution of Ni(NO₃)₂.6H₂ O. Pertinentinformation and data relating to the impregnation steps for each ofthese six catalysts are presented hereinbelow in Table XIX.

                                      TABLE XIX                                   __________________________________________________________________________    CATALYST IMPREGNATION DETAILS                                                 Catalyst     L   M   N    O    P   Q                                          __________________________________________________________________________    Support, gm  294 139 294  147  294 143                                        % molecular sieve                                                                          30  20  20   20   20  20                                         Type of molecular sieve                                                                    USAM                                                                              ZSM-5                                                                             AMS-1B                                                                             HEZ-55                                                                             DY  REY                                        First Impregnation                                                            Solution                                                                      (NH.sub.4).sub.2 Cr.sub.2 O.sub.7, gm                                                      66.4                                                                              25.2                                                                              66.4 33.2 66.4                                                                              33.2                                       Dist. H.sub.2 O, ml                                                                        300 120 270  100  200.sup.(3)                                    Standing                                                                      Time, hr     16  1   --   1    1   1                                          Temp., °C.                                                                          room                                                                              room                                                                              --   room room                                                                              room                                       Drying                                                                        Time, hr     --  --  --   2    16  2                                          Temp., °C.                                                                          --  --  --   121  121 121                                        Calcining                                                                     Time, hr     16  16  16.sup.(2)                                                                         16   >1  16                                         Temp., °C.                                                                          538 538 538  538  538 538                                        Second Impregnation                                                           Solution                                                                      (NH.sub.4).sub.6 Mo.sub.7 O.sub.24.4H.sub.2 O, gm                                          49.04                                                                             41.46                                                                             73.6 36.8 36.8                                                                              36.8                                       Ni(NO.sub.3).sub.2.6H.sub.2 O, gm                                                          --  27.07                                                                             --   27.25                                                                              11.68                                                                             27.25                                      Dist. H.sub.2 O, ml                                                                        250 100 200  90   110 90                                         Standing                                                                      Time, hr     6   --  --   1    1   1                                          Temp., °C.                                                                          room                                                                              room                                                                              room room room                                                                              room                                       Drying                                                                        Time, hr     --  --  --   1.5  --  2                                          Temp., °C.                                                                          --  --  --   121  --  121                                        Calcining                                                                     Time, hr     16  --  ≈60                                                                        16   --  16                                         Temp., °C.                                                                          538 538 538  538  --  538                                        Third Impregnation                                                            Solution                                                                      Ni(NO.sub.3).sub.2.6H.sub.2 O, gm                                                          11.68                                                                             --  27.25                                                                              --   15.57                                                                             --                                         Dist. H.sub.2 O, ml                                                                        125 --  100  --   100 --                                         Support, gm  182.5                                                                             --  190  --   166 --                                         Standing                                                                      Time, hr     6   --  --   --   --  --                                         Temp., °C.                                                                          room                                                                              --  --   --   room                                                                              --                                         Calcining                                                                     Time, hr     16  --  --   --   >1  --                                         Temp., °C.                                                                          538 --  538  --   538 --                                         Catalyst size, mesh (Tyler)                                                                16/20                                                                             16/20                                                                             14/20                                                                              14/20                                                                              14/20                                                                             14/20                                      __________________________________________________________________________     .sup.(1) 10 ml of 30% H.sub.2 O.sub.2 added to aid solution of                (NH.sub.4).sub.6 Mo.sub.7 O.sub.24.4H.sub.2 O.                                .sup.(2) Excess liquid decanted prior to calcination. Decanted liquid         added to calcined material, which was again calcined.                         .sup.(3) Additional distilled water used to make 250 ml of solution.     

Catalysts L, M, N, O, P, and Q were tested for their abilities tohydrotreat the heavy vacuum gas oil Feed No. 3 in Tests Nos. 13, 14, 15,16, 17, 18, and 19, respectively. The results of these tests arepresented hereinbelow in Tables XX, XXI, XXII, XXIII, XXIV, and XXV,respectively.

                  TABLE XX                                                        ______________________________________                                        DATA FOR TEST NO. 14, CATALYST L, FEED NO. 3                                  Days on Stream 6              8     13                                        ______________________________________                                        LHSV, hr.sup.-1                                                                              1.25           1.25  1.25                                      Temp., °F.                                                                            740            780   780                                       °C.     393            416   416                                       Hydrogen Pressure, psi                                                                       1,200          1,200 1,200                                     kPa            8,343          8,343 8,343                                     Hydrogen Rate, SCFB                                                                          13,300         14,500                                                                              14,500                                    m.sup.3 /m.sup.3                                                                             2,370          2,580 2,580                                     Product Properties                                                            Gravity, °API                                                                         26.2           31.0  29.8                                      gm/cc          0.8973         0.8708                                                                              0.8772                                    Pour Point, °F.                                                                       115            --    105                                       °C.     46             --    41                                        Viscosity at 100° C.,                                                                 5.57           --    3.11                                      cst                                                                           Carbon, wt %   87.16          --    87.12                                     Hydrogen, wt % 12.65          --    12.85                                     Sulfur, ppm    800            113   150                                       Nitrogen, ppm  483            105   160                                       Sim. Dist., °F. (°C.)                                           IBP            215     (102)  --    150    (66)                                5%            428     (220)  --    307   (153)                               20%            617     (325)  --    533   (279)                               50%            729     (387)  --    749   (398)                               80%            792     (422)  --    884   (473)                               95%            818     (437)  --    969   (521)                               HDS, %         97.3           99.6  99.1                                      HDN, %         71.6           93.8  90.5                                      Hydrogen Consumed,                                                                           580            --    755                                       SCFB                                                                          m.sup.3 /m.sup.3                                                                             103            --    134                                       Product Yield, wt %                                                           C.sub.1 -C.sub.4                                                                             0.4            --    1.3                                       IBP - 182° C.                                                                         3.1            --    7.4                                       182°-343° C.                                                                   23.1           --    25.4                                      343° C..sup.+                                                                         73.3           --    65.9                                      ______________________________________                                    

                  TABLE XXI                                                       ______________________________________                                        DATA FOR TEST NO. 15, CATALYST M, FEED NO. 3                                  Days on Stream 8              11    14                                        ______________________________________                                        LHSV, hr.sup.-1                                                                              1.25           1.25  1.25                                      Temp., °F.                                                                            740            780   780                                       °C.     393            416   416                                       Hydrogen Pressure, psi                                                                       1,200          1,200 1,200                                     kPa            8,343          8,343 8,343                                     Hydrogen Rate, SCFB                                                                          12,000         12,000                                                                              12,000                                    m.sup.3 /m.sup.3                                                                             2,140          2,140 2,140                                     Product Properties                                                            Gravity, °API                                                                         27.4           30.1  29.8                                      gm/cc          0.8905         0.8756                                                                              0.8772                                    Pour Point, °F.                                                                       70             --    -10                                       °C.     21.1           --    -23.3                                     Viscosity at 100° C.,                                                                 4.61           --    2.80                                      cst                                                                           Carbon, wt %   87.14          --    87.37                                     Hydrogen, wt % 12.78          --    12.61                                     Sulfur, ppm    285            74    80                                        Nitrogen, ppm  475            210   265                                       Sim. Dist., °F. (°C.)                                           IBP            164      (73)  --    110    (43)                                5%            404     (206)  --    270   (132)                               20%            652     (344)  --    534   (279)                               50%            803     (429)  --    741   (394)                               80%            913     (490)  --    875   (469)                               95%            995     (535)  --    961   (517)                               HDS, %         99.0           99.8  99.7                                      HDN, %         72.0           87.6  84.4                                      Hydrogen Consumed,                                                                           690            --    630                                       SCFB                                                                          m.sup.3 /m.sup.3                                                                             123            --    112                                       Product Yield, wt %                                                           C.sub.1 -C.sub.4                                                                             1.1            --    3.5                                       IBP - 182° C.                                                                         4.0            --    8.5                                       182°-343° C.                                                                   15.5           --    23.7                                      343° C..sup.+                                                                         79.3           --    64.3                                      ______________________________________                                    

                                      TABLE XXII                                  __________________________________________________________________________    DATA FOR TEST NO. 16, CATALYST N, FEED NO. 3                                  Days on Stream 1   5       7   11                                             __________________________________________________________________________    LHSV, hr.sup.-1                                                                              1.25                                                                              1.25    1.25                                                                              1.25                                           Temp., °F.                                                                            740 740     780 780                                            °C.     393 393     416 416                                            Hydrogen Pressure, psi                                                                       1,200                                                                             1,200   1,200                                                                             1,200                                          kPa            8,343                                                                             8,343   8,343                                                                             8,343                                          Hydrogen Rate, SCFB                                                                          13,000                                                                            13,000  16,000                                                                            16,000                                         m.sup.3 /m.sup.3                                                                             2,315                                                                             2,315   2,850                                                                             2,850                                          Product Properties                                                            Gravity, °API                                                                         28.1                                                                              27.4    30.7                                                                              29.8                                           gm/cc          0.8866                                                                            0.8905  0.8724                                                                            0.8772                                         Pour Point, °F.                                                                       --  80      --10                                                                              -5                                             °C.     --  26.7    --  -20.6                                          Viscosity at 100° C., cst                                                             --  4.91    --  2.91                                           Carbon, wt %   --  87.33   --  87.36                                          Hydrogen, wt % --  12.60   --  12.61                                          Sulfur, ppm    200 305     56  79                                             Nitrogen, ppm  256 415     170 210                                            Sim. Dist., °F. (°C.)                                           IBP            --  173  (79)                                                                             --  116  (47)                                       5%            --  409 (209)                                                                             --  275 (135)                                      20%            --  645 (341)                                                                             --  522 (272)                                      50%            --  736 (391)                                                                             --  721 (383)                                      80%            --  909 (487)                                                                             --  852 (455)                                      95%            --  994 (534)                                                                             --  942 (505)                                      HDS, %         99.3                                                                              99.0    99.8                                                                              99.7                                           HDN, %         84.9                                                                              75.6    90.0                                                                              87.6                                           Hydrogen Consumed, SCFB                                                                      --  555     --  610                                            m.sup.3 /m.sup.3                                                                             --  99      --  109                                            Product Yield, wt %                                                           C.sub.1 -C.sub.4                                                                             --  0.7     --  2.6                                            IBP - 182° C.                                                                         --  3.5     --  8.5                                            182°-343° C.                                                                   --  17.1    --  26.6                                           343° C..sup.+                                                                         --  78.7    --  62.3                                           __________________________________________________________________________

                                      TABLE XXIII                                 __________________________________________________________________________    DATA FOR TEST NO. 17, CATALYST O, FEED NO. 3                                  Days on Stream                                                                              3   7      10     12  14     17                                 __________________________________________________________________________    LHSV, hr.sup.-1                                                                             1.25                                                                              1.25   1.25   0.625                                                                             0.625  1.25                               Temp., °F.                                                                           740 740    780    780 780    740                                °C.    393 393    416    416 416    393                                Hydrogen Pressure, psi                                                                      1,200                                                                             1,200  1,200  1,200                                                                             1,200  1,200                              kPa           8,343                                                                             8,343  8,343  8,343                                                                             8,343  8,343                              Hydrogen Rate, SCFB                                                                         12,000                                                                            12,000 12,000 12,000                                                                            12,000 12,000                             m.sup.3 /m.sup.3                                                                            2,140                                                                             2,140  2,140  2,140                                                                             2,140  2,140                              Product Properties                                                            Gravity, °API                                                                        27.0                                                                              26.1   30.9   36.1                                                                              37.2   27.1                               gm/cc         0.8927                                                                            0.8978 0.8713 0.8443                                                                            0.8388 0.8922                             Pour Point, °F.                                                                      --  110    105    --  20     100                                °C.    --  43     41     --  -6.7   38                                 Viscosity at 100° C.,                                                                --  5.80   2.40   --  Low    5.90                               cst                                                                           Carbon, wt %  --  --     87.16  --  86.95  --                                 Hydrogen, wt %                                                                              --  --     12.80  --  13.05  --                                 Sulfur, ppm   --  1,050  160    44  49     1,460                              Nitrogen, ppm 558 603    147    75  30     649                                Sim. Dist., °F. (°C.)                                           IBP           --  223 (106)                                                                            170  (77)                                                                            --  132  (55)                                                                            243 (118)                           5%           --  505 (263)                                                                            354 (179)                                                                            --  199  (93)                                                                            537 (281)                          20%           --  702 (372)                                                                            588 (309)                                                                            --  319 (159)                                                                            715 (380)                          50%           --  830 (443)                                                                            769 (409)                                                                            --  521 (272)                                                                            843 (451)                          80%           --  935 (502)                                                                            895 (480)                                                                            --  754 (401)                                                                            959 (515)                          95%           --  --  (--)                                                                             984 (529)                                                                            --  868 (465)                                                                            --  (--)                           HDS, %        --  96.5   99.5   99.8                                                                              99.5   95.1                               HDN, %        67.1                                                                              64.5   91.3   93.5                                                                              98.2   61.8                               Hydrogen Consumed, SCFB                                                                     --  590    730    --  1,070  540                                m.sup.3 /m.sup.3                                                                            --  105    130    --  190    96                                 Product Yield, wt %                                                           C.sub.1 -C.sub.4                                                                            --  2.3    1.5    --  6.5    1.4                                IBP - 182° C.                                                                        --  1.9    5.1    --  24.3   1.7                                182°-343° C.                                                                  --  11.2   22.1   --  36.6   9.7                                343° C..sup.+                                                                            --  84.7   71.3   --  32.5   87.3                           __________________________________________________________________________

                                      TABLE XXIV                                  __________________________________________________________________________    DATA FOR TEST NO. 18, CATALYST P, FEED NO. 3                                  Days on Stream                                                                              8      13     16     20       23                                __________________________________________________________________________    LHSV, hr.sup.-1                                                                             1.25   0.612  1.25   0.612    1.25                              Temp., °F.                                                                           740    740    780    780      740                               °C.    393    393    416    416      393                               Hydrogen Pressure , psi                                                                     1,200  1,200  1,200  1,200    1,200                             kPa           8,343  8,343  8,343  8,343    8,343                             Hydrogen Rate, SCFB                                                                         12,000 12,000 12,000 12,000   12,000                            m.sup.3 /m.sup.3                                                                            2,140  2,140  2,140  2,140    2,140                             Product Properties                                                            Gravity, °API                                                                        27.3   36.6   30.4   64.4     26.4                              gm/cc         0.8911 0.8418 0.8740 0.7223   0.8961                            Pour Point, °F.                                                                      110    80     105    -60      105                               °C.    43     26.7   41     -51.1    41                                Viscosity at 100° C.,                                                                5.28   1.53   2.91   --       5.75                              cst                                                                           Carbon, wt %  87.06  86.61  87.08  87.26    87.01                             Hydrogen, wt %                                                                              12.74  13.37  12.90  14.29    12.93                             Sulfur, ppm   700    184    161    580      1,080                             Nitrogen, ppm 491    66     105    8.6      681                               Sim. Dist., °F. (°C.)                                           IBP           195  (91)                                                                            126 (52)                                                                             119  (48)                                                                            -17 (-27.2)                                                                            254 (123)                          5%           460 (238)                                                                            231 (111)                                                                            279 (137)                                                                            63  (17.2)                                                                             515 (269)                         20%           682 (361)                                                                            367 (186)                                                                            522 (272)                                                                            134 (56) 701 (372)                         50%           818 (437)                                                                            591 (311)                                                                            749 (398)                                                                            196 (91) 832 (444)                         80%           920 (493)                                                                            807 (431)                                                                            889 (476)                                                                            255 (124)                                                                              931 (500)                         95%           996 (536)                                                                            873 (468)                                                                            975 (524)                                                                            332 (167)                                                                              1,010                                                                             (543)                         HDS, %        97.7   99.4   99.5   98.0     96.3                              HDN, %        71.1   96.1   93.8   99.4     59.6                              Hydrogen Consumed, SCFB                                                                     683    1,150  862    2,200    780                               m.sup.3 /m.sup.3                                                                            122    205    154    392      139                               Product Yield, wt %                                                           C.sub.2 -C.sub.4                                                                            0.7    2.8    1.7    18.0     0.6                               IBP - 182° C.                                                                        2.7    16.5   8.4    78.7     1.7                               182°-343° C.                                                                  13.1   39.9   25.0   2.5      11.7                              343° C..sup.+                                                                        83.5   40.8   64.9   0.8      86.0                              __________________________________________________________________________

                                      TABLE XXV                                   __________________________________________________________________________    DATA FOR TEST NO. 19, CATALYST Q, FEED NO. 3                                  Days on Stream                                                                              4      7      11       18     21                                __________________________________________________________________________    LHSV, hr.sup.-1                                                                             1.25   1.25   0.625    0.625  1.25                              Temp., °F.                                                                           740    780    780      750    740                               °C.    393    416    416      399    393                               Hydrogen Pressure,                                                                          1,200  1,200  1,200    1,200  1,200                             psi                                                                           kPa           8,343  8,343  8,343    8,343  8,343                             Hydrogen Rate, SCFB                                                                         12,000 12,000 12,000   12,000 12,000                            m.sup.3 /m.sup.3                                                                            2,140  2,140  2,140    2,140  2,140                             Product Properties                                                            Gravity, °API                                                                        27.7   31.1   51.2     33.2   26.0                              gm/cc         0.8800 0.8708 0.7720   0.8591 0.8984                            Pour Point, °F.                                                                      90     95     -70      85     100                               °C.    32.2   35     -56.7    29.4   38                                Viscosity at 100° C., cst                                                            5.68   2.85   0.82     1.90   5.81                              Carbon, wt %  86.97  87.18  86.09    87.06  82.11                             Hydrogen, wt %                                                                              12.90  12.78  13.89    12.93  12.68                             Sulfur, ppm   810    190    254      52     1,270                             Nitrogen, ppm 535    123    1.6      22     800                               Sim. Dist., °F. (°C.)                                           IBP           295 (146)                                                                            117  (47)                                                                            -29 (-33.9)                                                                            117  (47)                                                                            104  (40)                          5%           510 (266)                                                                            284 (140)                                                                            115  (46)                                                                              242 (117)                                                                            270 (132)                         20%           688 (365)                                                                            525 (274)                                                                            199  (93)                                                                              438 (226)                                                                            582 (305)                         50%           817 (436)                                                                            747 (397)                                                                            295 (146)                                                                              653 (345)                                                                            998 (537)                         80%           917 (492)                                                                            886 (475)                                                                            415 (213)                                                                              842 (450)                                                                            930 (499)                         95%           994 (534)                                                                            971 (522)                                                                            536 (280)                                                                              945 (507)                                                                            --  (--)                          HDS, %        --     --     --       --     --                                HDN, %        68.5   92.7   99.9     98.7   52.3                              Hydrogen Consumed, SCFB                                                                     762    726    1,720    860    610                               m.sup.3 /m.sup.3                                                                            136    129    306      153    109                                Product Yield, wt %                                                          C.sub.1 -C.sub.4                                                                            0.6    1.6    9.7      2.9    0.5                               IBP - 182° C.                                                                        1.3    8.2    61.2     12.4   8.6                               182°-343° C.                                                                  13.3   24.6   28.5     35.7   17.6                              343° C..sup.-                                                                        84.8   65.6   0.6      49.0   73.2                              __________________________________________________________________________

The conversion data obtained with Catalysts J, L, M, N, O, P, and Q andpresented in Tables XV, XVI, and XX through XXV are summarizedhereinbelow in Tables XXVI and XXVII.

                                      TABLE XXVI                                  __________________________________________________________________________    SUMMARY OF CONVERSION DATA AT 740° F. (393° C.)                 __________________________________________________________________________            Catalyst                                                                      J            J   L   M    N     O          P        P                         Molecular Sieve                                                               NONE         NONE                                                                              USAM                                                                              HZSM-5                                                                             HAMS-1B                                                                             HEZ-55     DY       DY                        Days on Stream                                                                4   14 21 A  5   6   8    5     7    17 A  8  23 A  13                __________________________________________________________________________    LHSV, hr.sup.-1                                                                       0.625                                                                             0.625                                                                            0.625                                                                            0.625                                                                            1.25                                                                              1.25                                                                              1.25 1.25  1.25 1.25                                                                             1.25                                                                             1.25                                                                             1.25                                                                             1.25                                                                             0.612             C.sub.1 -C.sub.4, wt %                                                                0.9 0.7                                                                              0.9                                                                              0.8                                                                              0.6 0.4 1.1  0.7   2.3  1.4                                                                              1.9                                                                              0.7                                                                              0.6                                                                              0.7                                                                              2.8               IBP - 182° C.,                                                                 0.3 1.8                                                                              2.1                                                                              1.4                                                                              0.3 3.1 4.0  3.5   1.9  1.7                                                                              1.8                                                                              2.7                                                                              1.7                                                                              2.2                                                                              16.5              wt %                                                                          182°-343° C.,                                                           20.2                                                                              16.5                                                                             15.4                                                                             17.4                                                                             15.6                                                                              23.1                                                                              15.5 17.1  11.2 9.7                                                                              10.5                                                                             13.1                                                                             11.7                                                                             12.4                                                                             39.9              wt %                                                                          343° C..sup.+ , wt %                                                           78.6                                                                              81.0                                                                             81.5                                                                             80.3                                                                             83.5                                                                              73.3                                                                              79.3 78.7  84.7 87.3                                                                             86.0                                                                             83.5                                                                             86.0                                                                             84.8                                                                             40.8              __________________________________________________________________________                                                     Catalyst                                                                      Q.sup.(1)                                                                        Q                                                                          Molecular Sieve                                                               Rey                                                                              Rey                                                                        Days on Stream                                                                18 4  21 A                   __________________________________________________________________________                                           LHSV, hr.sup.-1                                                                         0.625                                                                            1.25                                                                             1.25                                                                             1.25                                                       C.sub.1 -C.sub.4, wt                                                                    2.9                                                                              0.6                                                                              0.5                                                                              0.6                                                        IBP - 182° C., wt                                                                   12.4                                                                             1.3                                                                              8.6                                                                              5.0                                                     182°-343° C.,                                                             35.7                                                                             13.3                                                                             17.6                                                                             15.5                                                       wt %                                                                          343° C..sup.+, wt                                                                49.0                                                                             84.8                                                                             73.2                                                                             79.0                __________________________________________________________________________     A = Arithmetic average of values shown                                        .sup.(1) = at 750° F. (399° C.)                            

                                      TABLE XXVII                                 __________________________________________________________________________    SUMMARY OF CONVERSION DATA AT 780° F. (416° C.)                           Catalyst                                                                      J   J      L       M    N     O    O    P   P  Q  Q                           Molecular Sieve                                                               NONE                                                                              NONE       USAM                                                                              HZSM-5                                                                             HAMS-1B                                                                             HEZ-55                                                                             HEZ-55                                                                             DY  DY REY                                                                              REY                         Days on Stream                                                                11  8   12 A   13  14   11    14   10   20  16 11 7                 __________________________________________________________________________    LHSV, hr.sup.-1                                                                         0.625                                                                             1.25                                                                              1.25                                                                             1.25                                                                              1.25                                                                              1.25 1.25  0.625                                                                              1.25 0.612                                                                             1.25                                                                             0.625                                                                            1.25              C.sub.1 -C.sub.4, wt %                                                                  2.2 0.6 1.4                                                                              1.0 1.3 3.5  2.6   6.5  1.5  18.0                                                                              1.7                                                                              9.7                                                                              1.6               IBP - 182° C., wt %                                                              3.4 1.2 4.1                                                                              2.7 7.4 8.5  8.5   24.3 5.1  78.7                                                                              8.4                                                                              61.2                                                                             8.2               182°-343° C., wt %                                                        31.3                                                                              13.7                                                                              28.2                                                                             21.0                                                                              25.4                                                                              23.7 26.6  36.6 22.1 2.5 25.0                                                                             28.5                                                                             24.6              343°  C..sup.+, wt %                                                             63.1                                                                              84.5                                                                              66.3                                                                             75.4                                                                              65.9                                                                              64.3 62.3  32.5 71.3 0.8 64.9                                                                             0.6                                                                              65.6              __________________________________________________________________________     A = Arithmetic average of values shown                                   

In each of these last two tables, where more than one set of values ispresented for a catalyst at the specified conditions, an arithmeticaverage of the values for each particular product component is presentedand this arithmetic average is the amount of that product componentconsidered hereinafter for that specified catalyst at the specifiedconditions.

Examination of the data in Tables XXVI and XXVII reveals that eachcatalyst containing a crystalline molecular sieve zeolite component ateither value of LHSV and a temperature of 780° F. (416° C.) provides aconversion of the hydrocarbon stream to lighter materials that isgreater than that furnished by the catalyst that has a support of onlyalumina and that does not contain a crystalline molecular sieve zeolite.At a temperature of 740° F. (393° C.) and an LHSV of 0.625 hr⁻¹, allthose catalysts containing a molecular sieve zeolite component that weretested at this value of LHSV provided conversions that were greater thanthe conversion furnished by the catalyst that did not contain acrystalline molecular sieve zeolite. Furthermore, in the case of thehigher LHSV and the lower temperature, the catalysts containingultrastable, large-pore crystalline aluminosilicate material, ZSM-5-typecrystalline aluminosilicates, AMS-1B crystalline borosilicates, or rareearth metal-exchanged crystalline Y-type aluminosilicates all tend toprovide a somewhat higher conversion than the conversion furnished bythe catalyst that does not contain a crystalline molecular sieve zeolitecomponent.

As shown by the data in Tables XX, XXI, XXII, XXIII, XXIV, and XXV, eachof Catalysts L, M, N, O, P, and Q is an effective catalyst for theprocess of the present invention for hydrotreating a heavy hydrocarbonstream containing a substantial amount of nitrogen compound to providemotor fuel components, heater oil components, and a feedstock for acatalytic cracking unit. Both nitrogen levels and sulfur levels that areacceptable for a catalytic cracker feed were obtained.

The tests involving Catalysts J, L, M, N, O, P, and Q demonstrate theembodiment of the process of the present invention wherein a heavyhydrocarbon stream containing a substantial amount of nitrogen compoundsis hydrodenitrogenated and hydrocracked to provide motor fuelcomponents, heater oil components, and a feedstock that is suitable fora catalytic cracking unit.

What is claimed is:
 1. A process for the hydrodenitrogenation andhydrocracking of a hydrocarbon stream containing a substantial amount ofnitrogen compounds, which process comprises contacting said stream in areaction zone under hydrodenitrogenation and hydrocracking conditionsand in the presence of hydrogen with a catalyst comprising ahydrogenation component comprising chromium, molybdenum, and at leastone Group VIII metal, a crystalline molecular sieve zeolite selectedfrom the group consisting of ZSM crystalline aluminosilicate and AMScrystalline metallosilicate and containing exchangeable cations, and aporous refractory inorganic oxide, the metals of said hydrogenationcomponent being present in the elemental form as oxides, as sulfides, ormixtures thereof, said stream being selected from the group consistingof petroleum hydrocarbon distillates, liquids derived from coal, liquidsderived from tar sands, and whole shale oil or any fraction of shaleoil.
 2. The process of claim 1, wherein said conditions comprise atemperature within the range of about 700° F. (371° C.) to about 800° F.(427° C.), a pressure within the range of about 1,000 psi (6,890 kPa) toabout 2,500 psi (17,225 kPa), an LHSV within the range of about 0.1volume of hydrocarbon per hour per volume of catalyst to about 5 volumesof hydrocarbon per hour per volume of catalyst, a hydrogen addition rateof hydrogen recycle rate within the range of about 2,000 SCFB (359 m³/m³) to about 20,000 SCFB (3,596 m³ /m³), and a hydrogen-to-hydrocarbonmolar ratio within the range of about 3 moles of hydrogen per mole ofhydrocarbon to about 60 moles of hydrogen per mole of hydrocarbon.
 3. Aprocess for the hydrodenitrogenation and hydrocracking of a hydrocarbonstream containing a substantial amount of nitrogen compounds, whichprocess comprises contacting said stream in a reaction zone underhydrodenitrogenation and hydrocracking conditions and in the presence ofhydrogen with a catalyst comprising a hydrogenation component comprisingchromium, molybdenum, and at least one Group VIII metal deposed upon asupport comprising a crystalline molecular sieve zeolite selected fromthe group consisting of a ZSM-5 crystalline aluminosilicate and anAMS-1B crystalline borosilicate suspended in and distributed throughouta matrix of a refractory inorganic oxide support material, the metals ofsaid hydrogenation component being present in the elemental form asoxides, as sulfides, or mixtures thereof, said stream being selectedfrom the group consisting of petroleum hydrocarbon distillates, liquidsderived from coal, liquids derived from tar sands, and whole shale oilor any fraction of shale oil.
 4. The process of claim 3, wherein saidconditions comprise a temperature within the range of about 700° F.(371° C.) to about 800° F. (427° C.), a pressure within the range ofabout 1,000 psi (6,890 kPa) to about 2,500 psi (17,225 kPa), an LHSVwithin the range of about 0.1 volume of hydrocarbon per hour per volumeof catalyst to about 5 volumes of hydrocarbon per hour per volume ofcatalyst, a hydrogen addition rate or hydrogen recycle rate within therange of about 2,000 SCFB (359 m³ /m³) to about 20,000 SCFB (3,596 m³/m³), and a hydrogen-to-hydrocarbon molar ratio within the range ofabout 3 moles of hydrogen per mole of hydrocarbon to about 60 moles ofhydrogen per mole of hydrocarbon.
 5. The process of claim 3, whereinsaid refractory inorganic oxide support material is an alumina, saidmetal of Group VIII is present in an amount within the range of about0.5 wt% to about 10 wt%, calculated as the oxide of the metal, saidmolybdenum is present in an amount within the range of about 5 wt% toabout 25 wt%, calculated as MoO₃, and said chromium is present in anamount within the range of about 3 wt% to about 15 wt%, calculated asCr₂ O₃, each amount being based upon the weight of said catalyst, andsaid molecular sieve zeolite is present in an amount within the range ofabout 5 wt% to about 90 wt%, based upon the weight of said support. 6.The process of claim 5, wherein said conditions comprise a temperaturewithin the range of about 700° F. (371° C.) to about 800° F. (427° C.),a pressure within the range of about 1,000 psi (6,890 kPa) to about2,500 psi (17,225 kPa), an LHSV within the range of about 0.1 volume ofhydrocarbon per hour per volume of catalyst to about 5 volumes ofhydrocarbon per hour per volume of catalyst, a hydrogen addition rate orhydrogen recycle rate within the range of about 2,000 SCFB (359 m³ /m³)to about 20,000 SCFB (3,596 m³ /m³), and a hydrogen-to-hydrocarbon molarratio within the range of about 3 moles of hydrogen per mole ofhydrocarbon to about 60 moles of hydrogen per mole of hydrocarbon. 7.The process of claim 5, wherein said Group VIII metal of said catalystis cobalt or nickel and said crystalline molecular sieve zeolite of saidcatalyst is an AMS-1B crystalline borosilicate.
 8. The process of claim7, wherein said conditions comprise a temperature within the range ofabout 700° F. (371° C.) to about 800° F. (427° C.), a pressure withinthe range of about 1,000 psi (6,890 kPa) to about 2,500 psi (17,225kPa), an LHSV within the range of about 0.1 volume of hydrocarbon perhour per volume of catalyst to about 5 volumes of hydrocarbon per hourper volume of catalyst, a hydrogen addition rate or hydrogen recyclerate within the range of about 2,000 SCFB (359 m³ /m³) to about 20,000SCFB (3,596 m³ /m³), and a hydrogen-to-hydrocarbon molar ratio withinthe range of about 3 moles of hydrogen per mole of hydrocarbon to about60 moles of hydrogen per mole of hydrocarbon.
 9. A process for thehydrodenitrogenation and hydrocracking of a hydrocarbon streamcomprising whole shale oil or any fraction thereof to produce jet fuelcomponents, which process comprises contacting said stream in a reactionzone under hydrodenitrogenation and hydrocracking conditions and in thepresence of hydrogen with a catalyst comprising a hydrogenationcomponent comprising chromium, molybdenum, and at least one Group VIIImetal, a crystalline molecular sieve zeolite selected from the groupconsisting of ZSM crystalline aluminosilicate and AMS crystallinemetallosilicate and containing exchangeable cations, and a porousrefractory inorganic oxide, the metals of said hydrogenation componentbeing present in the elemental form as oxides, as sulfides, or mixturesthereof.
 10. The process of claim 9, wherein said conditions comprise atemperature within the range of about 700° F. (371° C.) to about 800° F.(427° C.), a pressure within the range of about 1,000 psi (6,890 kPa) toabout 2,500 psi (17,225 kPa), an LHSV within the range of about 0.1volume of hydrocarbon per hour per volume of catalyst to about 5 volumesof hydrocarbon per hour per volume of catalyst, a hydrogen addition rateor hydrogen recycle rate within the range of about 2,000 SCFB (359 m³/m³) to about 20,000 SCFB (3,596 m³ /m³), and a hydrogen-to-hydrocarbonmolar ratio within the range of about 3 moles of hydrogen per mole ofhydrocarbon to about 60 moles of hydrogen per mole of hydrocarbon. 11.The process of claim 9, wherein said crystalline molecular sieve zeoliteof said catalyst is an AMS crystalline metallosilicate.
 12. The processof claim 11, wherein said conditions comprise a temperature within therange of about 700° F. (371° C.) to about 800° F. (427° C.), a pressurewithin the range of about 1,000 psi (6,890 kPa) to about 2,500 psi(17,225 kPa), an LHSV within the range of about 0.1 volume ofhydrocarbon per hour per volume of catalyst to about 5 volumes ofhydrocarbon per hour per volume of catalyst, a hydrogen addition rate orhydrogen recycle rate within the range of about 2,000 SCFB (359 m³ /m³)to about 20,000 SCFB (3,596 m³ /m³), and a hydrogen-to-hydrocarbon molarratio within the range of about 3 moles of hydrogen per mole ofhydrocarbon to about 60 moles of hydrogen per mole of hydrocarbon.
 13. Aprocess for the hydrodenitrogenation and hydrocracking of a hydrocarbonstream comprising whole shale oil or any fraction thereof to produce jetfuel components, which process comprises contacting said stream in areaction zone under hydrodenitrogenation and hydrocracking conditionsand in the presence of hydrogen with a catalyst comprising ahydrogenation component comprising chromium, molybdenum, and at leastone Group VIII metal deposed upon a support comprising a crystallinemolecular sieve zeolite selected from the group consisting of a ZSM-5crystalline aluminosilicate and an AMS-1B crystalline borosilicatesuspended in and distributed throughout a matrix of a high-surface arearefractory inorganic oxide support material, the metals of saidhydrogenation component being present in the elemental form as oxides,as sulfides, or mixtures thereof.
 14. The process of claim 13, whereinsaid conditions comprise a temperature within the range of about 700° F.(371° C.) to about 800° F. (427° C.), a pressure within the range ofabout 1,000 psi (6,890 kPa) to about 2,500 psi (17,225 kPa), an LHSVwithin the range of about 0.1 volume of hydrocarbon per hour per volumeof catalyst to about 5 volumes of hydrocarbon per hour per volume ofcatalyst, a hydrogen addition rate or hydrogen recycle rate within therange of about 2,000 SCFB (359 m³ /m³) to about 20,000 SCFB (3,596 m³/m³), and a hydrogen-to-hydrocarbon molar ratio within the range ofabout 3 moles of hydrogen per mole of hydrocarbon to about 60 moles ofhydrogen per mole of hydrocarbon.
 15. A process for thehydrodenitrogenation and hydrocracking of a whole shale oil or anyfraction thereof to produce jet fuel components, which process comprisescontacting said stream in a reaction zone under dehydrodenitrogenationand hydrocracking conditions and in the presence of hydrogen with acatalyst comprising a hydrogenation component comprising chromium,molybdenum, and at least one Group VIII metal deposed upon a supportcomprising a crystalline molecular sieve zeolite selected from the groupconsisting of a ZSM-5 crystalline aluminosilicate and an AMS-1Bcrystalline borosilicate suspended in and distributed throughout amatrix of an alumina, the metals of said hydrogenation component beingpresent in the elemental form as oxides, as sulfides, or mixturesthereof, said metal of Group VIII being present in an amount within therange of about 0.5 wt% to about 10 wt%, calculated as the oxide of themetal, said molybdenum being present in an amount within the range ofabout 5 wt% to about 25 wt%, calculated as MoO₃, and said chromium beingpresent in an amount within the range of about 3 wt% to about 15 wt%,calculated as Cr₂ O₃, each amount being based upon the weight of saidcatalyst, and said molecular sieve zeolite being present in an amountwithin the range of about 5 wt% to about 90 wt%, based upon the weightof said support.
 16. The process of claim 15, wherein said conditionscomprise a temperature within the range of about 700° F. (371° C.) toabout 800° F. (427° C.), a pressure within the range of about 1,000 psi(6,890 kPa) to about 2,500 psi (17,225 kPa), an LHSV within the range ofabout 0.1 volume of hydrocarbon per hour per volume of catalyst to about5 volumes of hydrocarbon per hour per volume of catalyst, a hydrogenaddition rate or hydrogen recycle rate within the range of about 2,000SCFB (359 m³ /m³) to about 20,000 SCFB (3,596 m³ /m³), and ahydrogen-to-hydrocarbon molar ratio within the range of about 3 moles ofhydrogen per mole of hydrocarbon to about 60 moles of hydrogen per moleof hydrocarbon.
 17. The process of claim 15, wherein said conditionscomprise a temperature within the range of about 740° F. (393° C.) toabout 790° F. (416° C.), a hydrogen partial pressure within the range ofabout 1,600 psi (11,024 kPa) to about 2,000 psi (13,780 kPa), an LHSVwithin the range of about 0.3 volume of hydrocarbon per hour per volumeof catalyst to about 2 volumes of hydrocarbon per hour per volume ofcatalyst, a hydrogen addition rate or hydrogen recycle rate within therange of about 6,000 SCFB (1,079 m³ /m³) to about 14,000 SCFB (2,517 m³/m³), and a hydrogen-to-hydrocarbon molar ratio within the range ofabout 10 moles of hydrogen per mole of hydrocarbon to about 30 moles ofhydrogen per mole of hydrocarbon.
 18. The process of claim 15, whereinsaid metal of Group VIII of said catalyst is cobalt or nickel.
 19. Theprocess of claim 18, wherein said conditions comprise a temperaturewithin the range of about 700° F. (371° C.) to about 800° F. (427° C.),a pressure within the range of about 1,000 psi (6,890 kPa) to about2,500 psi (17,225 kPa), an LHSV within the range of about 0.1 volume ofhydrocarbon per hour per volume of catalyst to about 5 volumes ofhydrocarbon per hour per volume of catalyst, a hydrogen addition rate orhydrogen recycle rate within the range of about 2,000 SCFB (359 m³ /m³)to about 20,000 SCFB (3,596 m³ /m³), and a hydrogen-to-hydrocarbon molarratio within the range of about 3 moles of hydrogen per mole ofhydrocarbon to about 60 moles of hydrogen per mole of hydrocarbon. 20.The process of claim 18, wherein said crystalline molecular sievezeolite of said catalyst is a ZSM-5 crystalline aluminosilicate.
 21. Theprocess of claim 20, wherein said conditions comprise a temperaturewithin the range of about 700° F. (371° C.) to about 800° F. (427° C.),a pressure within the range of about 1,000 psi (6,890 kPa) to about2,500 psi (17,225 kPa), an LHSV within the range of about 0.1 volume ofhydrocarbon per hour per volume of catalyst to about 5 volumes ofhydrocarbon per hour per volume of catalyst, a hydrogen addition rate orhydrogen recycle rate within the range of about 2,000 SCFB (359 m³ /m³)to about 20,000 SCFB (3,596 m³ /m³), and a hydrogen-to-hydrocarbon molarratio within the range of about 3 moles of hydrogen per mole ofhydrocarbon to about 60 moles of hydrogen per mole of hydrocarbon. 22.The process of claim 18, wherein said crystalline molecular sievezeolite of said catalyst is an AMS-1B crystalline borosilicate.
 23. Theprocess of claim 22, wherein said conditions comprise a temperaturewithin the range of about 700° F. (371° C.) to about 800° F. (427° C.),a pressure within the range of about 1,000 psi (6,890 kPa) to about2,500 psi (17,225 kPa), an LHSV within the range of about 0.1 volume ofhydrocarbon per hour per volume of catalyst to about 5 volumes ofhydrocarbon per hour per volume of catalyst, a hydrogen addition rate orhydrogen recycle rate within the range of about 2,000 SCFB (359 m³ /m³)to about 20,000 SCFB (3,596 m³ /m³), and a hydrogen-to-hydrocarbon molarratio within the range of about 3 moles of hydrogen per mole ofhydrocarbon to about 60 moles of hydrogen per mole of hydrocarbon.
 24. Aprocess for the hydrodenitrogenation and hydrocracking of a petroleumhydrocarbon distillate containing a substantial amount of nitrogencompounds to produce motor fuel components, heater oil components, and ahydrocarbon stream that is a suitable feedstock for a catalytic crackingunit, said distillate comprising heavy vacuum gas oils, light virgin gasoils, heavy coker gas oils, full-range gas oils, or mixtures thereof,which process comprises contacting said distillate in a reaction zoneunder hydrodenitrogenation and hydrocracking conditions and in thepresence of hydrogen with a catalyst comprising a hydrogenationcomponent comprising chromium, molybdenum, and at least one Group VIIImetal deposed upon a support comprising a crystalline molecular sievezeolite selected from the group consisting of a HAMS-1B crystallineborosilicate and a HZSM-5 crystalline aluminosilicate suspended in anddistributed throughout a matrix of a catalytically active alumina, themetals of said hydrogenation component being present in the elementalform, as oxides, as sulfides, or mixtures thereof, said metal of GroupVIII being present in an amount within the range of about 0.5 wt% toabout 10 wt%, calculated as the oxide of the metal, said molybdenumbeing present in an amount within the range of about 5 wt% to about 25wt%, calculated as MoO₃, and said chromium being present in an amountwithin the range of about 3 wt% to about 15wt%, calculated as Cr₂ O₃,each amount being based upon the weight of said catalyst, and saidmolecular sieve zeolite being present in an amount within the range ofabout 5 wt% to about 90 wt%, based upon the weight of said support. 25.The process of claim 24, wherein said conditions comprise a temperaturewithin the range of about 700° F. (371° C.) to about 800° F. (427° C.),a pressure within the range of about 1,000 psi (6,890 kPa) to about2,500 psi (17,225 kPa), an LHSV within the range of about 0.1 volume ofhydrocarbon per hour per volume of catalyst to about 5 volumes ofhydrocarbon per hour per volume of catalyst, a hydrogen addition rate orhydrogen recycle rate within the range of about 2,000 SCFB (359 m³ /m³)to about 20,000 SCFB (3,596 m³ /m³), and a hydrogen-to-hydrocarbon molarratio within the range of about 3 moles of hydrogen per mole ofhydrocarbon to about 60 moles of hydrogen per mole of hydrocarbon. 26.The process of claim 24, wherein said conditions comprise a temperaturewithin the range of about 740° F. (393° C.) to about 790° F. (416° C.),a hydrogen partial pressure within the range of about 1,600 psi (11,024kPa) to about 2,000 psi (13,780 kPa), an LHSV within the range of about0.3 volume of hydrocarbon per hour per volume of catalyst to about 2volumes of hydrocarbon per hour per volume of catalyst, a hydrogenaddition rate or hydrogen recycle rate within the range of about 6,000SCFB (1,079 m³ /m³) to about 14,000 SCFB (2,517 m³ /m³), and ahydrogen-to-hydrocarbon molar ratio within the range of about 10 molesof hydrogen per mole of hydrocarbon to about 30 moles of hydrogen permole of hydrocarbon.
 27. The process of claims 24, wherein said GroupVIII metal of said catalyst is nickel.
 28. The process of claim 27,wherein said conditions comprise a temperature within the range of about700° F. (371° C.) to about 800° F. (427° C.), a pressure within therange of about 1,000 psi (6,890 kPa) to about 2,500 psi (17,225 kPa),and LHSV within the range of about 0.1 volume of hydrocarbon per hourper volume of catalyst to about 5 volumes of hydrocarbon per hour pervolume of catalyst, a hydrogen addition rate or hydrogen recycle ratewithin the range of about 2,000 SCFB (359 m³ /m³) to about 20,000 SCFB(3,596 m³ /m³), and a hydrogen-to-hydrocarbon molar ratio within therange of about 3 moles of hydrogen per mole of hydrocarbon to about 60moles of hydrogen per mole of hydrocarbon.
 29. The process of claims 24,wherein said Group VIII metal of said catalyst is cobalt.
 30. Theprocess of claim 29, wherein said conditions comprise a temperaturewithin the range of about 700° F. (371° C.) to about 800° F. (427° C.),a pressure within the range of about 1,000 psi (6,890 kPa) to about2,500 psi (17,225 kPa), an LHSV within the range of about 0.1 volume ofhydrocarbon per hour per volume of catalyst to about 5 volumes ofhydrocarbon per hour per volume of catalyst, a hydrogen addition rate ofhydrogen recycle rate within the range of about 2,000 SCFB (359 m³ /m³)to about 20,000 SCFB (3,596 m³ /m³), and a hydrogen-to-hydrocarbon molarratio within the range of about 3 moles of hydrogen per mole ofhydrocarbon to about 60 moles of hydrogen per mole of hydrocarbon. 31.The process of claim 24, wherein said crystalline molecular sievezeolite is a HAMS-1B crystalline borosilicate.
 32. The process of claim31, wherein said conditions comprise a temperature within the range ofabout 700° F. (371° C.) to about 800° F. (427° C.), a pressure withinthe range of about 1,000 psi (6,890 kPa) to about 2,500 psi (17,225kPa), an LHSV within the range of about 0.1 volume of hydrocarbon perhour per volume of catalyst to about 5 volumes of hydrocarbon per hourper volume of catalyst, a hydrogen addition rate or hydrogen recyclerate within the range of about 2,000 SCFB (359 m³ /m³) to about 20,000SCFB (3,596 m³ /m³), and a hydrogen-to-hydrocarbon molar ratio withinthe range of about 3 moles of hydrogen per mole of hydrocarbon to about60 moles of hydrogen per mole of hydrocarbon.
 33. The process of claim31, wherein said distillate is a heavy vacuum gas oil.
 34. The processof claim 33, wherein said conditions comprise a temperature within therange of about 740° F. (393° C.) to about 790° F. (416° C.), a hydrogenpartial pressure within the range of about 1,600 psi (11,024 kPa) toabout 2,000 psi (13,780 kPa), an LHSV within the range of about 0.3volume of hydrocarbon per hour per volume of catalyst to about 2 volumesof hydrocarbon per hour per volume of catalyst, a hydrogen addition rateor hydrogen recycle rate within the range of about 6,000 SCFB (1,079 m³/m³) to about 14,000 SCFB (2,517 m³ /m³), and a hydrogen-to-hydrocarbonmolar ratio within the range of about 10 moles of hydrogen per mole ofhydrocarbon to about 30 moles of hydrogen per mole of hydrocarbon. 35.The process of claim 24, wherein said crystalline molecular sievezeolite is an HZSM-5 crystalline aluminosilicate.
 36. The process ofclaim 35, wherein said distillate is a heavy vacuum gas oil.
 37. Theprocess of claim 36, wherein said conditions comprise a temperaturewithin the range of about 700° F. (371° C.) to about 800° F. (427° C.),a pressure within the range of about 1,000 psi (6,890 kPa) to about2,500 psi (17,225 kPa), an LHSV within the range of about 0.1 volume ofhydrocarbon per hour per volume of catalyst to about 5 volumes ofhydrocarbon per hour per volume of catalyst, a hydrogen addition rate orhydrogen recycle rate within the range of about 2,000 SCFB (359 m³ /m³)to about 20,000 SCFB (3,596 m³ /m³), and a hydrogen-to-hydrocarbon molarratio within the range of about 3 moles of hydrogen per mole ofhydrocarbon to about 60 moles of hydrogen per mole of hydrocarbon.